UIO-66-NH2-Pt-coated TpPa heterostructure material with photocatalytic performance and preparation method of UIO-66-NH2-Pt-coated TpPa heterostructure material

Abstract

The invention discloses a UIO-66-NH2-Pt at TpPa heterostructure material with photocatalytic performance and a preparation method thereof, the heterostructure is composed of an octahedron-like UIO material and TpPa on the octahedron-like UIO material, and a TpPa nano layer is formed on the outer side of the UIO and is in a winding and wrapping shape; the preparation method of the heterostructure comprises the following three steps: carrying out hydro-thermal synthesis on UIO-66-NH2 of a mixed monodentate ligand, preparing a platinum single atom anchored UIO-66-NH2-Pt material, and finally synthesizing the UIO-66-NH2-Pt-coated TpPa heterojunction material through a condensation reaction. According to the invention, chlorine groups are introduced in a breakthrough manner to regulate electron transfer, so that the utilization rate of photon-generated carriers is remarkably improved, and the photocatalytic hydrogen production efficiency is improved; the photocatalytic water splitting hydrogen production performance is excellent, good chemical stability is achieved, and the potential of achieving low-cost and large-scale application is achieved.

Description

(1) Technical field:

[0001] The present invention relates to the field of photocatalytic water hydrogen production, and specifically to a heterojunction material formed by a metal organic framework loaded with platinum single atoms and a covalent organic framework and a preparation method thereof, namely, a UIO-66-NH2-Pt@TpPa heterostructure material with photocatalytic performance and a preparation method thereof. (2) Background technology:

[0002] The overuse of fossil fuels has exacerbated the current resource crisis, prompting the rapid development of clean and renewable energy as a viable alternative energy source. Light-driven water splitting to produce hydrogen is an attractive reaction that can easily obtain the required clean energy. [1] .

[0003] Catalyst optimization is an eternal topic in this field. Currently, researchers have explored a variety of methods, such as constructing heterogeneous structures. [2] , interface engineering [3] , introduce co-catalyst [4] However, in most traditional catalysts, the transport distance of photogenerated electrons to active sites is random, resulting in low electron utilization and inefficient separation of photogenerated carriers. Therefore, optimizing the transport pathway of photogenerated electrons will help improve photocatalytic activity.

[0004] Metal-organic frameworks (MOFs) are a class of porous materials with a periodic network structure composed of customizable metal nodes and organic ligands. [5] This predictable structure makes MOFs a candidate material for establishing electron transport channel systems. Recently, heterostructures constructed by covalently linked MOFs-NH2 and COFs have shown excellent hydrogen production efficiency. [6] At the same time, covalent organic frameworks (COFs) have short band gaps and strong light absorption, so they can act as photosensitizers and electron reservoirs, absorbing light and transferring electrons in heterostructures. However, how to construct a clear electron transfer pathway to the active site and how to regulate it in a targeted manner remains challenging.

[0005] The present invention uses 3-amino-2-chloroisonicotinic acid as a monodentate ligand to modify UIO-66-NH2 to form a MOF material containing a large number of defects, thereby providing active sites for the anchoring of single platinum atoms. The composite with COF further improves the mobility and utilization of carriers, enhances its adsorption of reaction intermediates, and improves the activity of the catalyst.

[0006] References:

[0007] 1.Herran,M.;Juergensen,S.;Kessens,M.;Hoeing,D.; A.;Sousa-Castillo,A.;Parak,W.J.;Lange,H.;Reich,S.;Schulz,F.,Cortés,E.;PlasmonicBimetallic Two-Dimensional Supercrystals for H2 Generation.Nat.Catal.2023,6,1205-1214.

[0008] 2.Luan,B.-B.;Chu,X.;Wang,Y.;Qiao,X.;Jiang,Y.,Zhang,F.-M.;Constructionof COF / COF Organic S-Scheme Heterostructure for Enhanced Overall WaterSplitting.Adv.Mater.2024,36,2412653.

[0009] 3.Yu,Y.;Zhu,Z.,Huang,H.;Surface Engineered Single-Atom Systems forEnergy Conversion.Adv.Mater.2024,36,2311148.

[0010] 4.Tao,X.;Zhao,Y.;Wang,S.;Li,C.,Li,R.;Recent Advances and Perspectivesfor Solar-Driven Water Splitting using Particulate Photocatalysts.Chem.Soc.Rev.2022,51,3561-3608.

[0011] 5.Furukawa,H.;Cordova,K.E.;O’Keeffe,M.,Yaghi,O.M.;The Chemistry andApplications of Metal-Organic Frameworks.Science 2013,341,1230444.

[0012] 6.Chen, C.-X.; Xiong, Y.-Y.; Zhong, Composites. Angew. Chem. Int. Ed. 2022, 61, e202114071. (3) Summary of the invention:

[0013] The purpose of the present invention is to provide a UIO-66-NH2-Pt@TpPa heterostructure material with photocatalytic performance and a preparation method thereof, which can solve the technical problems of serious carrier recombination, low separation efficiency, and low utilization rate of photogenerated electron holes in metal organic framework-based photocatalysts. It can effectively improve the specific surface area electron transfer efficiency of the catalyst material, fully improve the utilization rate of carriers, have excellent photocatalytic water hydrogen production performance, and have good chemical stability.

[0014] In order to solve the above technical problems, the present invention is achieved through the following technical solutions: a UIO-66-NH2-Pt@TpPa heterostructure material with photocatalytic performance, including a defective UIO-66-NH2 synthesized by replacing part of aminoterephthalic acid with 3-amino-2-chloroisonicotinic acid; single platinum atoms are introduced on UIO-66-NH2 to form Pt-N / O chemical bonds; TpPa material is introduced on the surface of UIO-66-NH2-Pt to form a UIO-66-NH2-Pt@TpPa heterocomposite material.

[0015] The diameter of the UIO-66-NH2 is 300-400 nm;

[0016] The diameter of the platinum single atom is 0.1-0.3 nm;

[0017] The thickness of the TpPa is 500-600 nm;

[0018] The diameter of the UIO-66-NH2-Pt@TpPa material is 1.0-1.5 μm.

[0019] The UIO-66-NH2-Pt@TpPa heterogeneous composite material is a heterogeneous structure composed of UIO-66-NH2 nanomaterials and TpPa nanolayers, and the TpPa nanosheets grow on the surface of the UIO nanomaterials.

[0020] A method for preparing a UIO-66-NH2-Pt@TpPa heterostructure material with photocatalytic hydrogen production performance comprises the following steps:

[0021] (1) Preparation of UIO-66-NH2 material: In a reaction tube, zirconium tetrachloride powder, aminoterephthalic acid powder, and 3-amino-2-chloroisonicotinic acid monodentate ligand powder were added to DMF and mixed and stirred evenly, and then hydrothermal synthesis was performed to obtain defective UIO-66-NH2 powder;

[0022] (2) Preparation of UIO-66-NH2-Pt material: adding the defective UIO-66-NH2 powder obtained in step (1) to DMF, adding chloroplatinic acid, and then reacting in a water bath to obtain UIO-66-NH2-Pt powder containing single platinum atoms;

[0023] (3) Preparation of UIO-66-NH2-Pt@TpPa heterostructure material: ① Add the UIO-66-NH2-Pt powder and trialdehyde phloroglucinol powder obtained in step (2) to DMF and mix them evenly. Then add p-phenylenediamine powder and add 200 μL 6M acetic acid per mL of DMF to disperse them evenly.

[0024] ② The reaction tube obtained in step ① was quickly frozen in a liquid N2 bath with a vacuum valve, degassed through a freeze-evacuation-thaw cycle, sealed under vacuum, and subjected to a heating condensation reaction; finally, the collected powder was UIO-66-NH2-Pt@TpPa.

[0025] In the step (1), the mass ratio of the zirconium tetrachloride powder, the aminoterephthalic acid powder and the 3-amino-2-chloroisonicotinic acid monodentate ligand powder is 100:30:11 to 100:120:44.

[0026] In the step (1), the zirconium tetrachloride powder, aminoterephthalic acid powder and 3-amino-2-chloroisonicotinic acid monodentate ligand powder are added to DMF and dissolved by ultrasonication for 10 minutes.

[0027] The hydrothermal synthesis reaction in step (1) is carried out at 80-160° C. for 6-24 hours.

[0028] The mass ratio of the defective UIO-66-NH2 powder to chloroplatinic acid in step (2) is 10:0.1 to 10:4.

[0029] The water bath reaction in step (2) is carried out at 50-120° C. for 6-24 hours.

[0030] In step (2), the defective UIO-66-NH2 powder is added to DMF and dissolved by ultrasonication for 5 minutes.

[0031] In the step (3), the mass ratio of UIO-66-NH2-Pt, trialdehyde phloroglucinol and p-phenylenediamine powder is 6:3:2 to 6:12:10.

[0032] The heating reaction in step (4) is carried out at a heating temperature of 50-120° C. for 3-24 hours.

[0033] A UIO-66-NH2-Pt@TpPa composite material with photocatalytic hydrogen evolution performance is used to photocatalytically decompose deionized water to generate hydrogen.

[0034] A method for using a UIO-66-NH2-Pt@TpPa composite material with photocatalytic hydrogen evolution performance to photocatalytically decompose deionized water to generate hydrogen is as follows:

[0035] ① UIO-66-NH2-Pt@TpPa was suspended in a PBS aqueous solution containing sodium ascorbate as a sacrificial electron donor and irradiated with visible light;

[0036] ② Before the photocatalytic reaction, the reaction vessel is evacuated to remove dissolved gases and ensure vacuum conditions; during the entire photocatalytic process, the reaction system is maintained at a certain temperature.

[0037] The beneficial effects of the present invention are:

[0038] The target material UIO-66-NH2-Pt@TpPa described in the present invention has a heterogeneous structure, which greatly improves the carrier separation efficiency compared with traditional metal-organic framework-based photocatalytic materials, increases the carrier utilization rate and light absorption, and improves the utilization rate of the material; the present invention has excellent performance in photolysis of water to produce hydrogen, good chemical stability, and has the potential for low-cost, large-scale application.

[0039] The UIO-66-NH2 containing monodentate ligand defects described in the present invention has abundant sites for Pt single atom anchoring, which can effectively increase the number of active sites and allow the water reduction reaction to occur at relatively low current intensity and low overpotential, thereby improving the hydrogen production efficiency; its further heterostructure with TpPa can accelerate the separation of carriers, allowing photogenerated electrons and holes to be quickly extracted, effectively reducing the possibility of electron and hole recombination.

[0040] Compared with traditional photocatalysts, UIO-66-NH2-Pt@TpPa material provides a novel single-atom loading synthesis concept, provides a new idea for the preparation of efficient heterojunction photocatalysts, and contributes to the development of MOF-COF photocatalytic semiconductor materials with simple production process and high hydrogen production efficiency.

[0041] The UIO-66-NH2-Pt@TpPa nanoheterostructure described in the present invention can be used as a highly efficient photocatalytic material, specifically for photocatalytic water production of hydrogen, which can efficiently convert solar energy into clean energy, effectively alleviating the current shortage of fossil fuels and severe environmental pollution. (4) Description of the accompanying drawings:

[0042] Figure 1 is a scanning electron microscope image of the defective UIO-66-NH2 powder in Example 1, with a scale of 1 μm;

[0043] Figure 2 is a transmission electron microscopy image of UIO-66-NH2-Pt@TpPa in Example 1, with a scale of 500 nm;

[0044] Figure 3 This is a spherical aberration-corrected electron micrograph of UIO-66-NH2-Pt@TpPa in Example 1, with a scale of 5 nm;

[0045] Figure 4 is the X-ray diffraction pattern of UIO-66-NH2-Pt@TpPa in Example 1;

[0046] Figure 5 2 is a hydrogen production rate curve of the UIO-66-NH2-Pt@TpPa heterostructure material prepared in Example 1 under visible light;

[0047] Figure 6 This is a bar chart of the hydrogen production rate of the UIO-66-NH2-Pt@TpPa heterostructure materials prepared in Examples 1-9 under visible light. (V) Specific implementation methods:

[0048] The present invention will be further described in detail below through specific examples. The following examples may enable those skilled in the art to have a more comprehensive understanding of the present invention, but are not intended to limit the present invention in any way.

[0049] Example 1: A UIO-66-NH2-Pt@TpPa heterostructure material with photocatalytic properties, including defective UIO-66-NH2 synthesized by replacing part of aminoterephthalic acid with 3-amino-2-chloroisonicotinic acid; single platinum atoms are introduced on the defective UIO-66-NH2 to form Pt-N / O chemical bonds; TpPa material is introduced on the surface of UIO-66-NH2-Pt to form a UIO-66-NH2-Pt@TpPa heterocomposite material.

[0050] The diameter of the defect UIO-66-NH2 is 300-400 nm;

[0051] The diameter of the platinum single atom is 0.1-0.3 nm;

[0052] The thickness of the TpPa is 500-600 nm;

[0053] The diameter of the UIO-66-NH2-Pt@TpPa material is 1.0-1.5 μm.

[0054] The UIO-66-NH2-Pt@TpPa heterogeneous composite material is a heterogeneous structure composed of UIO-66-NH2 nanomaterials and TpPa nanolayers, and the TpPa nanosheets grow on the surface of the UIO nanomaterials.

[0055] A method for preparing a UIO-66-NH2-Pt@TpPa heterostructure material with photocatalytic hydrogen production performance comprises the following steps:

[0056] (1) Preparation of defective UIO-66-NH2 containing monodentate ligands:

[0057] First, 102.5 mg of zirconium tetrachloride powder, 63.2 mg of aminoterephthalic acid, and 22.48 mg of 3-amino-2-chloroisonicotinic acid powder (mass ratio of 100:61:22) were added to 5 mL of DMF and ultrasonicated for 5 minutes to obtain a precursor solution. Using a hydrothermal synthesis method, the precursor solution was placed in a reactor and heated at 120°C for 12 hours. After the reaction was cooled to room temperature, the powder was collected by centrifugation and washed three times with DMF and methanol to obtain defective UIO-66-NH2 powder.

[0058] (2) Preparation of UIO-66-NH2-Pt:

[0059] 10 mg of the above-mentioned defective UIO-66-NH2 powder was mixed with 5 mL of DMF and ultrasonicated for 5 minutes. 0.5 mg of chloroplatinic acid (mass ratio of 10:0.5) was added and ultrasonicated for 5 minutes. The mixture was reacted at 85 ° C for 12 hours. After the reaction was cooled to room temperature, the powder was collected by centrifugation and washed three times with ethanol to obtain UIO-66-NH2-Pt powder containing single platinum atoms.

[0060] (3) Preparation of UIO-66-NH2-Pt@TpPa:

[0061] ① Weigh 6 mg of the defective UIO-66-NH2-Pt powder prepared in step (2) and 6.5 mg of trialdehyde phloroglucinol powder, add them to a reaction tube containing 0.5 mL of DMF, and sonicate for 10 minutes to mix them evenly;

[0062] ② Add 5 mg of p-phenylenediamine powder and 100 μL of 6 M acetic acid to the above solution (the mass ratio of UIO-66-NH2-Pt, trialdehyde phloroglucinol and p-phenylenediamine powder is 6:6.5:5), and sonicate for 10 minutes to mix evenly.

[0063] ③ The reaction tube obtained above was quickly frozen with a vacuum valve in a liquid N2 bath (77K), degassed through three freeze-evacuation-thaw cycles, sealed under vacuum, and heated at 85°C for 6 hours. After the reaction cooled to room temperature, the powder was collected by centrifugation and washed three times with DMF and ethanol, respectively, to obtain UIO-66-NH2-Pt@TpPa.

[0064] Figure 1 This is a scanning electron microscope image of the defective UIO-66-NH2 powder prepared in Example 1, with a scale of 1 μm.

[0065] As shown in the scanning electron microscopy image, the prepared UIO has an octahedral morphology and a size of 300-400 nm.

[0066] Figure 2 This is the transmission electron microscopy image of UIO-66-NH2-Pt@TpPa prepared in Example 1, with a scale of 500 nm.

[0067] As shown in the transmission electron microscopy image, TpPa grows tightly around UIO in a tangled and wrapped shape, presenting a heterostructure, which proves the successful synthesis of its heterostructure.

[0068] Figure 3 This is the spherical aberration correction diagram of UIO-66-NH2-Pt@TpPa prepared in Example 1, with a scale of 5 nm.

[0069] As shown in the spherical aberration-corrected electron microscope image, atomically dispersed platinum single atom bright spots with a diameter of 0.1-0.3 nm can be found on the MOFs, and no obvious platinum clusters or particles are observed, proving the successful synthesis of platinum single atoms.

[0070] Figure 4 This is the X-ray diffraction pattern of UIO-66-NH2-Pt@TpPa prepared in Example 1.

[0071] As shown in the X-ray diffraction pattern, the peaks before 10° are attributed to the crystal planes of UIO, while the peaks between 20° and 30° are attributed to the crystal planes of TpPa. The simultaneous presence of diffraction peaks of UIO and TpPa in the X-ray diffraction pattern indicates that the UIO-66-NH2-Pt@TpPa structure contains both UIO and TpPa, thus demonstrating the successful synthesis of the heterostructure.

[0072] (1) UIO-66-NH2-Pt@TpPa for photocatalytic water splitting to produce hydrogen

[0073] ① 3 mg of previously prepared UIO-66-NH2-Pt@TpPa was suspended in 25 mL of PBS (0.1 M, pH 7) containing 50 mg of sodium ascorbate as a sacrificial electron donor. A 300 W xenon lamp with a CUT400 filter was used to generate simulated visible light. The light intensity at the working electrode of the photoelectrochemical cell was measured by a radiometer to be 100 mW / cm 2 ;

[0074] ② Before the photocatalytic reaction, the reaction vessel was evacuated for 30 minutes to remove dissolved gases and ensure vacuum conditions. During the entire photocatalytic process, the reaction system was maintained at 6°C under the action of circulating condensate.

[0075] Figure 5 The hydrogen production rate curve of UIO-66-NH2-Pt@TpPa as a catalyst under visible light in Example 1. The experimental results show that the hydrogen production rate of UIO-66-NH2-Pt is 360 μmol g -1 h -1 ; while the hydrogen production rate of TpPa was only 231.8 μmol g -1 h -1 The hydrogen production rate of UIO-66-NH2-Pt@TpPa material is 14200 μmol g -1 h -1 , which is 61.25 times that of TpPa. This proves that the UIO-66-NH2-Pt@TpPa heterojunction material prepared in this example has greatly improved the performance of catalyzing water hydrogen production compared to traditional photocatalysts, and is an excellent catalyst material in photocatalytic water splitting hydrogen production.

[0076] Example 2: A UIO-66-NH2-Pt@TpPa heterostructure material with photocatalytic properties, including defective UIO-66-NH2 synthesized by replacing part of aminoterephthalic acid with 3-amino-2-chloroisonicotinic acid; single platinum atoms are introduced on UIO-66-NH2 to form Pt-N / O chemical bonds; TpPa material is introduced on the surface of UIO-66-NH2-Pt to form a UIO-66-NH2-Pt@TpPa heterocomposite material.

[0077] The diameter of the UIO-66-NH2 is 300-400 nm;

[0078] The diameter of the platinum single atom is 0.1-0.3 nm;

[0079] The thickness of the TpPa is 500-600 nm;

[0080] The diameter of the UIO-66-NH2-Pt@TpPa material is 1.0-1.5 μm.

[0081] The UIO-66-NH2-Pt@TpPa heterogeneous composite material is a heterogeneous structure composed of UIO-66-NH2 nanomaterials and TpPa nanolayers, and the TpPa nanosheets grow on the surface of the UIO nanomaterials.

[0082] A method for preparing a UIO-66-NH2-Pt@TpPa heterostructure material with photocatalytic hydrogen production performance comprises the following steps:

[0083] (1) The preparation of defective UIO-66-NH2 containing a monodentate ligand was the same as in Example 1;

[0084] (2) The preparation of UIO-66-NH2-Pt was the same as in Example 1;

[0085] (3) The preparation of UIO-66-NH2-Pt@TpPa was the same as in Example 1;

[0086] ① Weigh 6 mg of UIO-66-NH2-Pt powder and 6.5 mg of trialdehyde phloroglucinol powder prepared in step (2), add them to a reaction tube containing 0.5 mL of DMF, and sonicate for 10 minutes to mix them evenly;

[0087] ② Add 5 mg of p-phenylenediamine powder and 100 μL of 6M acetic acid to the above solution (the mass ratio of UIO-66-NH2-Pt, trialdehyde phloroglucinol and p-phenylenediamine powder is 6:6.5:5), and sonicate for 10 minutes to mix evenly;

[0088] ③ The reaction tube obtained above was quickly frozen with a vacuum valve in a liquid N2 bath (77K), degassed through three freeze-evacuation-thaw cycles, sealed under vacuum, and heated at 50°C for 6 h. After the reaction cooled to room temperature, the powder was collected by centrifugation and washed three times with DMF and ethanol, respectively, to obtain UIO-66-NH2-Pt@TpPa.

[0089] The results of transmission electron microscopy experiments show that the octahedral UIO nanostructure and the sheet-like TpPa are tightly bound to each other in a heterostructure. The size of UIO is 300-400nm, and the TpPa nanostructure grows near the middle UIO in a entangled and wrapped shape.

[0090] The photoelectrochemical performance test showed that the hydrogen production rate of this example was 10840 μmol g -1 h -1 .

[0091] Example 3: A UIO-66-NH2-Pt@TpPa heterostructure material with photocatalytic properties, including defective UIO-66-NH2 synthesized by replacing part of aminoterephthalic acid with 3-amino-2-chloroisonicotinic acid; single platinum atoms are introduced on UIO-66-NH2 to form Pt-N / O chemical bonds; TpPa material is introduced on the surface of UIO-66-NH2-Pt to form a UIO-66-NH2-Pt@TpPa heterocomposite material.

[0092] The diameter of the UIO-66-NH2 is 300-400 nm;

[0093] The diameter of the platinum single atom is 0.1-0.3 nm;

[0094] The thickness of the TpPa is 500-600 nm;

[0095] The diameter of the UIO-66-NH2-Pt@TpPa material is 1.0-1.5 μm.

[0096] The UIO-66-NH2-Pt@TpPa heterogeneous composite material is a heterogeneous structure composed of UIO-66-NH2 nanomaterials and TpPa nanolayers, and the TpPa nanosheets grow on the surface of the UIO nanomaterials.

[0097] A method for preparing a UIO-66-NH2-Pt@TpPa heterostructure material with photocatalytic hydrogen production performance comprises the following steps:

[0098] (1) The preparation of defective UIO-66-NH2 containing a monodentate ligand was the same as in Example 1;

[0099] (2) The preparation of UIO-66-NH2-Pt was the same as in Example 1;

[0100] (3) Preparation of UIO-66-NH2-Pt@TpPa:

[0101] ① Weigh 6 mg of UIO-66-NH2-Pt powder and 6.5 mg of trialdehyde phloroglucinol powder prepared in step (2), add them to a reaction tube containing 0.5 mL of DMF, and sonicate for 10 minutes to mix them evenly;

[0102] ② Add 5 mg of p-phenylenediamine powder and 100 μL of 6M acetic acid to the above solution (the mass ratio of UIO-66-NH2-Pt, trialdehyde phloroglucinol and p-phenylenediamine powder is 6:6.5:5), and sonicate for 10 minutes to mix evenly;

[0103] ③ The reaction tube obtained above was quickly frozen with a vacuum valve in a liquid N2 bath (77K), degassed through three freeze-evacuation-thaw cycles, sealed under vacuum, and heated at 120°C for 6 hours. After the reaction cooled to room temperature, the powder was collected by centrifugation and washed three times with DMF and ethanol, respectively, to obtain UIO-66-NH2-Pt@TpPa.

[0104] The results of transmission electron microscopy experiments show that the octahedral UIO nanostructure and the flake TpPa are tightly bound to each other in a heterostructure. The size of UIO is 300-400nm. TpPa nanostructures grow in a tangled and wrapped shape near the middle UIO, and black Pt particles are generated near UIO.

[0105] The photocatalytic hydrogen production performance test showed that the hydrogen production rate of this example was 9800 μmol g -1 h -1 .

[0106] Example 4: A UIO-66-NH2-Pt@TpPa heterostructure material with photocatalytic properties, including defective UIO-66-NH2 synthesized by replacing part of aminoterephthalic acid with 3-amino-2-chloroisonicotinic acid; single platinum atoms are introduced on the UIO-66-NH2 to form Pt-N / O chemical bonds; TpPa material is introduced on the surface of UIO-66-NH2-Pt to form a UIO-66-NH2-Pt@TpPa heterocomposite material.

[0107] The diameter of the UIO-66-NH2 is 300-400 nm;

[0108] The diameter of the platinum single atom is 0.1-0.3 nm;

[0109] The thickness of the TpPa is 500-600 nm;

[0110] The diameter of the UIO-66-NH2-Pt@TpPa material is 1.0-1.5 μm.

[0111] The UIO-66-NH2-Pt@TpPa heterogeneous composite material is a heterogeneous structure composed of UIO-66-NH2 nanomaterials and TpPa nanolayers, and the TpPa nanosheets grow on the surface of the UIO nanomaterials.

[0112] A method for preparing a UIO-66-NH2-Pt@TpPa heterostructure material with photocatalytic hydrogen production performance comprises the following steps:

[0113] (1) The preparation of defective UIO-66-NH2 containing a monodentate ligand was the same as in Example 1;

[0114] (2) The preparation of UIO-66-NH2-Pt was the same as in Example 1;

[0115] (3) Preparation of UIO-66-NH2-Pt@TpPa

[0116] ① Weigh 6 mg of UIO-66-NH2-Pt powder and 6.5 mg of trialdehyde phloroglucinol powder prepared in step (2), add them to a reaction tube containing 0.5 mL of DMF solution, and sonicate for 10 minutes to mix them evenly;

[0117] ② Add 5 mg of p-phenylenediamine powder and 100 μL of 6M acetic acid to the above solution (the mass ratio of UIO-66-NH2-Pt, trialdehyde phloroglucinol and p-phenylenediamine powder is 6:6.5:5), and sonicate for 10 minutes to mix evenly;

[0118] ③ The reaction tube obtained above was quickly frozen with a vacuum valve in a liquid N2 bath (77K), degassed through three freeze-evacuation-thaw cycles, sealed under vacuum, and heated at 85°C for 3 hours. After the reaction cooled to room temperature, the powder was collected by centrifugation and washed three times with DMF and ethanol, respectively, to obtain UIO-66-NH2-Pt@TpPa.

[0119] The results of transmission electron microscopy experiments show that the octahedral UIO nanostructure and the flake TpPa are tightly bound to each other in a heterostructure. The size of UIO is 300-400nm. TpPa nanostructures grow in a tangled and wrapped shape near the middle UIO, and black Pt particles are generated near UIO.

[0120] The photocatalytic hydrogen production performance test showed that the hydrogen production rate of this example was 11000 μmol g -1 h -1 .

[0121] Example 5: A UIO-66-NH2-Pt@TpPa heterostructure material with photocatalytic properties, including defective UIO-66-NH2 synthesized by replacing part of aminoterephthalic acid with 3-amino-2-chloroisonicotinic acid; single platinum atoms are introduced on UIO-66-NH2 to form Pt-N / O chemical bonds; TpPa material is introduced on the surface of UIO-66-NH2-Pt to form a UIO-66-NH2-Pt@TpPa heterocomposite material.

[0122] The diameter of the UIO-66-NH2 is 300-400 nm;

[0123] The diameter of the platinum single atom is 0.1-0.3 nm;

[0124] The thickness of the TpPa is 500-600 nm;

[0125] The diameter of the UIO-66-NH2-Pt@TpPa material is 1.0-1.5 μm.

[0126] The UIO-66-NH2-Pt@TpPa heterogeneous composite material is a heterogeneous structure composed of UIO-66-NH2 nanomaterials and TpPa nanolayers, and the TpPa nanosheets grow on the surface of the UIO nanomaterials.

[0127] A method for preparing a UIO-66-NH2-Pt@TpPa heterostructure material with photocatalytic hydrogen production performance comprises the following steps:

[0128] (1) The preparation of defective UIO-66-NH2 containing a monodentate ligand was the same as in Example 1;

[0129] (2) The preparation of UIO-66-NH2-Pt was the same as in Example 1;

[0130] (3) Preparation of UIO-66-NH2-Pt@TpPa

[0131] ① Weigh 6 mg of UIO-66-NH2-Pt powder and 7.8 mg of trialdehyde phloroglucinol powder prepared in step (2), add them to a reaction tube containing 0.5 mL of DMF solution, and sonicate for 10 minutes to mix them evenly;

[0132] ② Add 5 mg of p-phenylenediamine powder and 100 μL of 6 M acetic acid to the above solution (the mass ratio of UIO-66-NH2-Pt, trialdehyde phloroglucinol to p-phenylenediamine powder is 6:7.8:5), and sonicate for 10 minutes to mix evenly;

[0133] ③ The reaction tube obtained above was quickly frozen with a vacuum valve in a liquid N2 bath (77K), degassed through three freeze-evacuation-thaw cycles, sealed under vacuum, and heated at 85°C for 24 hours. After the reaction cooled to room temperature, the powder was collected by centrifugation and washed three times with DMF and ethanol, respectively, to obtain UIO-66-NH2-Pt@TpPa.

[0134] The results of transmission electron microscopy experiments show that the octahedral UIO nanostructure and the flake TpPa are tightly bound to each other in a heterostructure. The size of UIO is 300-400nm. TpPa nanostructures grow in a tangled and wrapped shape near the middle UIO, and black Pt particles are generated near UIO.

[0135] The photocatalytic hydrogen production performance test showed that the hydrogen production rate of this example was 7320 μmol g -1 h -1 .

[0136] Example 6: A UIO-66-NH2-Pt@TpPa heterostructure material with photocatalytic properties, including defective UIO-66-NH2 synthesized by replacing part of aminoterephthalic acid with 3-amino-2-chloroisonicotinic acid; single platinum atoms are introduced on the UIO-66-NH2 to form Pt-N / O chemical bonds; TpPa material is introduced on the surface of UIO-66-NH2-Pt to form a UIO-66-NH2-Pt@TpPa heterocomposite material.

[0137] The diameter of the UIO-66-NH2 is 300-400 nm;

[0138] The diameter of the platinum single atom is 0.1-0.3 nm;

[0139] The thickness of the TpPa is 500-600 nm;

[0140] The diameter of the UIO-66-NH2-Pt@TpPa material is 1.0-1.5 μm.

[0141] The UIO-66-NH2-Pt@TpPa heterogeneous composite material is a heterogeneous structure composed of UIO-66-NH2 nanomaterials and TpPa nanolayers, and the TpPa nanosheets grow on the surface of the UIO nanomaterials.

[0142] A method for preparing a UIO-66-NH2-Pt@TpPa heterostructure material with photocatalytic hydrogen production performance comprises the following steps:

[0143] (1) The preparation of defective UIO-66-NH2 containing a monodentate ligand was the same as in Example 1;

[0144] (2) Preparation of UIO-66-NH2-Pt

[0145] 10 mg of UIO powder was mixed with 5 mL of DMF and ultrasonicated for 5 minutes. 0.5 mg of chloroplatinic acid (mass ratio of 10:0.5) was added and ultrasonicated for 15 minutes. The mixture was reacted at 50°C for 12 hours. After the reaction was cooled to room temperature, the powder was collected by centrifugation and washed three times with ethanol to obtain UIO-66-NH2-Pt powder containing single platinum atoms.

[0146] (3) The preparation of UIO-66-NH2-Pt@TpPa was the same as in Example 1;

[0147] Transmission electron microscopy experimental results show that the octahedral UIO nanostructure and the sheet-like TpPa are tightly bound to each other in a heterostructure, and the size of UIO is 300-400nm.

[0148] The photocatalytic hydrogen production performance test showed that the hydrogen production rate of this example was 3200 μmol g-1 h -1 .

[0149] Example 7: A UIO-66-NH2-Pt@TpPa heterostructure material with photocatalytic properties, including defective UIO-66-NH2 synthesized by replacing part of aminoterephthalic acid with 3-amino-2-chloroisonicotinic acid; introducing single platinum atoms on UIO-66-NH2 to form Pt-N / O chemical bonds; and introducing TpPa material on the surface of UIO-66-NH2-Pt to form a UIO-66-NH2-Pt@TpPa heterocomposite material.

[0150] The diameter of the UIO-66-NH2 is 300-400 nm;

[0151] The diameter of the platinum single atom is 0.1-0.3 nm;

[0152] The thickness of the TpPa is 500-600 nm;

[0153] The diameter of the UIO-66-NH2-Pt@TpPa material is 1.0-1.5 μm.

[0154] The UIO-66-NH2-Pt@TpPa heterogeneous composite material is a heterogeneous structure composed of UIO-66-NH2 nanomaterials and TpPa nanolayers, and the TpPa nanosheets grow on the surface of the UIO nanomaterial in a entangled and wrapped shape.

[0155] A method for preparing a UIO-66-NH2-Pt@TpPa heterostructure material with photocatalytic hydrogen production performance comprises the following steps:

[0156] (1) The preparation of defective UIO-66-NH2 containing a monodentate ligand was the same as in Example 1;

[0157] (2) The preparation of UIO-66-NH2-Pt was the same as in Example 6;

[0158] 10 mg of UIO powder was mixed with 5 mL of DMF and ultrasonicated for 5 minutes. 0.5 mg of chloroplatinic acid (mass ratio of 10:0.5) was added and ultrasonicated for 15 minutes. The mixture was reacted at 120°C for 12 hours. After the reaction was cooled to room temperature, the powder was collected by centrifugation and washed three times with ethanol to obtain UIO-66-NH2-Pt powder containing single platinum atoms.

[0159] (3) The preparation of UIO-66-NH2-Pt@TpPa was the same as in Example 1;

[0160] The results of transmission electron microscopy experiments show that the octahedral UIO nanostructure and the flake TpPa are tightly bound to each other in a heterostructure. The size of UIO is 300-400nm. TpPa nanostructures grow in a tangled and wrapped shape near the middle UIO, and black Pt particles are generated near UIO.

[0161] The photocatalytic hydrogen production performance test showed that the hydrogen production rate of this example was 8542 μmol g -1 h -1 .

[0162] Example 8: A UIO-66-NH2-Pt@TpPa heterostructure material with photocatalytic properties, including defective UIO-66-NH2 synthesized by replacing part of aminoterephthalic acid with 3-amino-2-chloroisonicotinic acid; single platinum atoms are introduced on the UIO-66-NH2 to form Pt-N / O chemical bonds; TpPa material is introduced on the surface of UIO-66-NH2-Pt to form a UIO-66-NH2-Pt@TpPa heterocomposite material.

[0163] The diameter of the UIO-66-NH2 is 300-400 nm;

[0164] The diameter of the platinum single atom is 0.1-0.3 nm;

[0165] The thickness of the TpPa is 500-600 nm;

[0166] The diameter of the UIO-66-NH2-Pt@TpPa material is 1.0-1.5 μm.

[0167] The UIO-66-NH2-Pt@TpPa heterogeneous composite material is a heterogeneous structure composed of UIO-66-NH2 nanomaterials and TpPa nanolayers, and the TpPa nanosheets grow on the surface of the UIO nanomaterials.

[0168] A method for preparing a UIO-66-NH2-Pt@TpPa heterostructure material with photocatalytic hydrogen production performance comprises the following steps:

[0169] (1) Preparation of defective UIO-66-NH2 containing a monodentate ligand:

[0170] First, 102.5 mg of zirconium tetrachloride powder, 63.2 mg of aminoterephthalic acid, and 22.48 mg of 3-amino-2-chloroisonicotinic acid powder were added to 5 mL of DMF (mass ratio of 100:61:22) and sonicated for 5 minutes to obtain a precursor solution. Using a hydrothermal synthesis method, the precursor solution was placed in a reactor and heated at 80°C for 24 hours. After the reaction was cooled to room temperature, the powder was collected by centrifugation and washed three times with DMF and methanol.

[0171] (2) Preparation of UIO-66-NH2-Pt:

[0172] 10 mg of UIO powder was mixed with 5 mL of DMF and ultrasonicated for 5 minutes. 0.5 mg of chloroplatinic acid (mass ratio of 10:0.5) was added and ultrasonicated for 15 minutes. The mixture was reacted at 85 °C for 6 hours. After the reaction was cooled to room temperature, the powder was collected by centrifugation and washed three times with ethanol to obtain UIO-66-NH2-Pt powder containing single platinum atoms.

[0173] (3) Preparation of UIO-66-NH2-Pt@TpPa:

[0174] ① Weigh 6 mg of UIO-66-NH2-Pt powder and 3 mg of trialdehyde phloroglucinol powder prepared in step (2), add them to a reaction tube containing 0.5 mL of DMF solution, and sonicate for 10 minutes to mix them evenly;

[0175] ② Add 5 mg of p-phenylenediamine powder and 100 μL of 6 M acetic acid to the above solution and sonicate for 10 minutes (the mass ratio of UIO-66-NH2-Pt, trialdehyde phloroglucinol to p-phenylenediamine powder is 6:3:5) to mix them evenly.

[0176] ③ The reaction tube obtained above was quickly frozen with a vacuum valve in a liquid N2 bath (77K), degassed through three freeze-pump-thaw cycles, sealed under vacuum, and heated at 85°C for 12 hours. After the reaction cooled to room temperature, the powder was collected by centrifugation and washed three times with DMF and ethanol, respectively, to obtain UIO-66-NH2-Pt@TpPa.

[0177] The results of transmission electron microscopy experiments show that the octahedral UIO nanostructure and the flake TpPa are tightly bound to each other in a heterostructure. The size of UIO is 300-400nm. TpPa nanostructures grow in a tangled and wrapped shape near the middle UIO, and black Pt particles are generated near UIO.

[0178] The photocatalytic hydrogen production performance test showed that the hydrogen production rate of this example was 3600 μmol g -1 h -1 .

[0179] Example 9: A UIO-66-NH2-Pt@TpPa heterostructure material with photocatalytic properties, including defective UIO-66-NH2 synthesized by replacing part of aminoterephthalic acid with 3-amino-2-chloroisonicotinic acid; single platinum atoms are introduced on the UIO-66-NH2 to form Pt-N / O chemical bonds; TpPa material is introduced on the surface of UIO-66-NH2-Pt to form a UIO-66-NH2-Pt@TpPa heterocomposite material.

[0180] The diameter of the UIO-66-NH2 is 300-400 nm;

[0181] The diameter of the platinum single atom is 0.1-0.3 nm;

[0182] The thickness of the TpPa is 500-600 nm;

[0183] The diameter of the UIO-66-NH2-Pt@TpPa material is 1.0-1.5 μm.

[0184] The UIO-66-NH2-Pt@TpPa heterogeneous composite material is a heterogeneous structure composed of UIO-66-NH2 nanomaterials and TpPa nanolayers, and the TpPa nanosheets grow on the surface of the UIO nanomaterials.

[0185] A method for preparing a UIO-66-NH2-Pt@TpPa heterostructure material with photocatalytic hydrogen production performance comprises the following steps:

[0186] (1) Preparation of defective UIO-66-NH2 containing a monodentate ligand:

[0187] First, 102.5 mg of zirconium tetrachloride powder, 63.2 mg of aminoterephthalic acid, and 22.48 mg of 3-amino-2-chloroisonicotinic acid powder were added to 5 mL of DMF (mass ratio of 100:61:22) and ultrasonicated for 5 minutes to obtain a precursor solution. Using a hydrothermal synthesis method, the precursor solution was placed in a reactor and heated at 160°C for 6 hours. After the reaction was cooled to room temperature, the powder was collected by centrifugation and washed three times with DMF and methanol to obtain defective UIO-66-NH2 powder.

[0188] (2) Preparation of UIO-66-NH2-Pt:

[0189] 10 mg of UIO powder was mixed with 5 mL of DMF and ultrasonicated for 5 minutes. 0.5 mg of chloroplatinic acid (mass ratio of 10:0.5) was added and ultrasonicated for 15 minutes. The mixture was reacted at 85°C for 24 hours. After the reaction was cooled to room temperature, the powder was collected by centrifugation and washed three times with ethanol to obtain UIO-66-NH2-Pt powder containing single platinum atoms.

[0190] (3) Preparation of UIO-66-NH2-Pt@TpPa:

[0191] ① Weigh 6 mg of UIO-66-NH2-Pt powder and 12 mg of trialdehyde phloroglucinol powder prepared in step (2), add them to a reaction tube containing 0.5 mL of DMF solution, and sonicate for 10 minutes to mix them evenly;

[0192] ② Add 5 mg of p-phenylenediamine powder and 100 μL of 6 M acetic acid to the above solution (the mass ratio of UIO-66-NH2-Pt, trialdehyde phloroglucinol and p-phenylenediamine powder is 6:12:5), and sonicate for 10 minutes to mix evenly;

[0193] ③ The reaction tube obtained above was quickly frozen with a vacuum valve in a liquid N2 bath (77K), degassed through three freeze-evacuation-thaw cycles, sealed under vacuum, and heated at 85°C for 6 hours. After the reaction cooled to room temperature, the powder was collected by centrifugation and washed three times with DMF and ethanol, respectively, to obtain UIO-66-NH2-Pt@TpPa.

[0194] Transmission electron microscopy experimental results show that the octahedral UIO nanostructure and the sheet-like TpPa are tightly bound to each other in a heterostructure, and the size of UIO is 300-400nm.

[0195] The photocatalytic hydrogen production performance test showed that the hydrogen production rate of this example was 4953 μmol g -1 h -1 .

[0196] Although the preferred embodiments of the present invention have been described above in conjunction with the accompanying drawings, the present invention is not limited to the above-mentioned specific embodiments. The above-mentioned specific embodiments are merely illustrative and not restrictive. Under the guidance of the present invention, ordinary technicians in this field can also make many forms of specific changes without departing from the scope of protection of the present invention and the claims, which all fall within the scope of protection of the present invention.

Claims

1. A UIO-66-NH2-Pt@TpPa heterostructure material with photocatalytic performance, characterized in that It includes synthesizing defective UIO-66-NH2 by replacing part of aminoterephthalic acid with 3-amino-2-chloroisonicotinic acid; introducing single platinum atoms on UIO-66-NH2 to form Pt-N / O chemical bonds; and introducing TpPa material on the surface of UIO-66-NH2-Pt to form a UIO-66-NH2-Pt@TpPa heterogeneous composite material.

2. The UIO-66-NH2-Pt@TpPa heterostructure material with photocatalytic performance according to claim 1, characterized in that The diameter of the UIO-66-NH2 is 300-400 nm; The diameter of the platinum single atom is 0.1-0.3 nm; The thickness of the TpPa is 500-600 nm; The diameter of the UIO-66-NH2-Pt@TpPa material is 1.0-1.5 μm.

3. The UIO-66-NH2-Pt@TpPa heterostructure material with photocatalytic performance according to claim 1, characterized in that The UIO-66-NH2-Pt@TpPa heterogeneous composite material is a heterogeneous structure composed of UIO-66-NH2 nanomaterials and TpPa nanolayers, and the TpPa nanosheets grow on the surface of the UIO nanomaterials.

4. A method for preparing a UIO-66-NH2-Pt@TpPa heterostructure material with photocatalytic hydrogen production performance, characterized in that It includes the following steps: (1) Preparation of UIO-66-NH2 material: In a reaction tube, zirconium tetrachloride powder, aminoterephthalic acid powder, and 3-amino-2-chloroisonicotinic acid monodentate ligand powder were added to DMF and mixed and stirred evenly, and then hydrothermal synthesis was performed to obtain defective UIO-66-NH2 powder; (2) Preparation of UIO-66-NH2-Pt material: adding the defective UIO-66-NH2 powder obtained in step (1) to DMF, adding chloroplatinic acid, and reacting in a water bath to obtain UIO-66-NH2-Pt powder containing single platinum atoms; (3) Preparation of UIO-66-NH2-Pt@TpPa heterostructure material: ① Add the UIO-66-NH2-Pt powder and trialdehyde phloroglucinol powder obtained in step (2) to DMF and mix them evenly. Then add p-phenylenediamine powder and add 200 μL 6M acetic acid per mL of DMF to disperse them evenly. ② The reaction tube obtained in step ① was quickly frozen in a liquid N2 bath with a vacuum valve, degassed through a freeze-evacuation-thaw cycle, sealed under vacuum, and subjected to a heating condensation reaction; finally, the collected powder was UIO-66-NH2-Pt@TpPa.

5. The method for preparing the UIO-66-NH2-Pt@TpPa heterostructure material with photocatalytic hydrogen production performance according to claim 4, characterized in that In the step (1), the mass ratio of the zirconium tetrachloride powder, the aminoterephthalic acid powder and the 3-amino-2-chloroisonicotinic acid monodentate ligand powder is 100:30:11 to 100:120:

44.

6. The method for preparing the UIO-66-NH2-Pt@TpPa heterostructure material with photocatalytic hydrogen production performance according to claim 4, characterized in that The mass ratio of the defective UIO-66-NH2 powder to chloroplatinic acid in step (2) is 10:0.1 to 10:

4.

7. The method for preparing a UIO-66-NH2-Pt@TpPa heterostructure material having photocatalytic hydrogen production performance according to claim 4, characterized in that In the step (3), the mass ratio of UIO-66-NH2-Pt, trialdehyde phloroglucinol and p-phenylenediamine powder is 6:3:2 to 6:12:

10.

8. The method for preparing the UIO-66-NH2-Pt@TpPa heterostructure material with photocatalytic hydrogen production performance according to claim 4, characterized in that In the step (1), the zirconium tetrachloride powder, aminoterephthalic acid powder and 3-amino-2-chloroisonicotinic acid monodentate ligand powder are added to DMF and dissolved by ultrasonication for 10 minutes; The hydrothermal synthesis reaction in step (1) is carried out at 80-160° C. for 6-24 hours; The water bath reaction in step (2) is carried out at 50-120° C. for 6-24 hours; In step (2), the defective UIO-66-NH2 powder is added to DMF and dissolved by ultrasonication for 5 minutes; The heating reaction in step (3) is carried out at a heating temperature of 50-120° C. for 3-24 hours.

9. Application of UIO-66-NH2-Pt@TpPa heterostructure material with photocatalytic hydrogen production performance, characterized in that It is used for photocatalytic decomposition of deionized water to generate hydrogen.

10. The use of the UIO-66-NH2-Pt@TpPa heterostructure material with photocatalytic hydrogen production performance according to claim 9, characterized in that The method for producing hydrogen by photolysis of water is: ① UIO-66-NH2-Pt@TpPa was suspended in a PBS aqueous solution containing sodium ascorbate as a sacrificial electron donor and irradiated with visible light; ② Before the photocatalytic reaction, the reaction vessel is evacuated to remove dissolved gases and ensure vacuum conditions; during the entire photocatalytic process, the reaction system is maintained at a certain temperature.

Images