CN110560172A - Zirconium metal organic framework heterojunction material with photocatalytic performance and preparation method thereof - Google Patents

Zirconium metal organic framework heterojunction material with photocatalytic performance and preparation method thereof Download PDF

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CN110560172A
CN110560172A CN201910873404.4A CN201910873404A CN110560172A CN 110560172 A CN110560172 A CN 110560172A CN 201910873404 A CN201910873404 A CN 201910873404A CN 110560172 A CN110560172 A CN 110560172A
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卜显和
张冀杰
白田宇
于美慧
王禹婷
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Nankai University
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Abstract

The invention discloses a zirconium metal organic framework heterojunction material with photocatalytic performance and a preparation method thereof, and the zirconium metal organic framework heterojunction material NH with octahedron2-UiO-66 is coated with Pt nano particles inside, and MnO is deposited on the outer surface of the materialxThe integral appearance of the nano layer is in the shape of octahedron with a core-shell structure. The preparation method of the zirconium-based metal organic framework heterojunction material comprises the steps of preparing a Pt nano particle material and preparing NH coated with the Pt nano particle2-UiO-66 material (Pt @ NH)2-UiO-66), preparation of outer layer deposited MnOxPt @ NH of nanolayers2-UiO-66 material (Pt @ NH)2‑UiO‑66@MnOx) And (4) three steps. The invention utilizes the characteristic that the metal organic framework material has large specific surface area to load the space separation type Pt nano particles and MnOxThe nano layer is respectively used as a reduction promoter and an oxidation promoter, so that the separation efficiency of photon-generated carriers is improved, the hydrogen production activity and the chemical stability of water through photocatalytic decomposition are excellent, the preparation method is simple, and the large-scale application can be realized.

Description

Zirconium metal organic framework heterojunction material with photocatalytic performance and preparation method thereof
Technical Field
the invention relates to the field of semiconductor material design for hydrogen production by photocatalytic water decomposition, in particular to a zirconium metal organic framework heterojunction material and a preparation method thereof.
background
The energy crisis and the environmental pollution are increasingly serious, and people are urgently required to search clean and renewable green energy to replace the traditional fossil energy1. Solar energy is the most potential alternative of fossil energy due to its advantages of wide energy source, huge reserves, cleanness, no pollution and the like. How to effectively convert, store and reasonably utilize solar energy is always a problem to be solved urgently by scientific researchers.
In 1972, Fujishima and Honda reported that TiO was exposed to UV light2after decomposing water to produce hydrogen, the scientific community has generated great interest in the photocatalysis method2. The photocatalytic reaction can convert reactants such as water and carbon dioxide into clean energy such as hydrogen and methanol by utilizing the light absorption characteristics of semiconductor materials, so that solar energy is converted and stored into chemical energy. The photocatalysts now under investigation have focused primarily on inorganic metal oxide materials, such as TiO2、ZnO、WO3Etc. of3. The inorganic metal oxide photocatalyst has the advantages of wide precursor sources, mature preparation process, theoretical basis of system research and the like, and lays the firm position of the material in a photocatalytic system. However, researchers are not satisfied with the current situation, and the research on novel high-efficiency photocatalysts has not been stopped. In recent years, some metal organic framework Materials (MOFs) with semiconductor properties are beginning to be applied to photocatalytic reactions4. The material is formed by self-assembling metal ions or metal cluster units and organic ligands through coordinationThe porous crystalline material with the periodical multidimensional network structure has the characteristics of high crystallinity, high porosity, large specific surface area, adjustable structure composition and the like, and is widely applied to the fields of gas adsorption and separation, fluorescence, drug conduction, heterogeneous catalysis and the like5. Compared with the traditional inorganic metal oxide semiconductor material, the MOFs has two advantages: firstly, a space separation type core-shell structure is easy to form, and the core-shell structure heterojunction photocatalyst is easier to prepare6(ii) a Secondly, the MOFs structure has high orderliness, designability and tailorability to a certain degree, and the highly developed pore structure ensures that the MOFs structure has ultrahigh specific surface area and more surface reaction active sites7. Not negligible, MOFs photocatalysts also have similar drawbacks as traditional inorganic oxide semiconductor materials: the insufficient utilization rate of light energy in a visible light region, faster recombination of photoproduction electron holes, poor water stability and the like always restrict the photocatalytic performance of the composite material8. Among them, how to accelerate the reaction kinetics of the photocatalytic surface is always the focus of research on MOFs photocatalyst9。
1.A.Kudo and Y.Miseki,Heterogeneous Photocatalyst Materials for Water Splitting,Chem.Soc.Rev.,2009,38,253-278.
2.A.Fujishima and K.Honda,Electrochemical Photolysis of Water at A Semiconductor Electrode,Nature,1972,238,37-38.
3.J.Barber,Photosynthetic Energy Conversion:Natural and Artificial,Chem.Soc.Rev.,2009,38,185-196.
4.G.Huang,Y.Chen and H.Jiang,Metal-Organic Frameworks for Catalysis,Acta Chimica Sinica,2016,74,113.
5.Y.Cui,B.Li,H.He,W.Zhou,B.Chen and G.Qian,Metal-Organic Frameworks as Platforms for Functional Materials,Acc.Chem.Res.,2016,49,483-493.
6.Y.Liu and Z.Tang,Multifunctional Nanoparticle@MOF Core-shell Nanostructures,Adv.Mater.,2013,25,5819-5825.
7.A.Dhakshinamoorthy,A.M.Asiri and H.Garcia,Metal-Organic Framework(MOF)Compounds:Photocatalysts for Redox Reactions and Solar Fuel Production,Angew.Chem.Int.Ed.,2016,55,5414-5445.
8.T.Zhang and W.Lin,Metal-organic Frameworks for Artificial Photosynthesis and Photocatalysis,Chem.Soc.Rev.,2014,43,5982-5993.
9.K.Meyer,M.Ranocchiari and J.A.van Bokhoven,Metal Organic Frameworks forPhoto-catalytic Water Splitting,EnergyEnviron.Sci.,2015,8,1923-1937.
Disclosure of Invention
The invention aims to solve the problem of zirconium metal organic framework material NH2The UiO-66 has the problems of high carrier recombination probability and slow reaction kinetics in the photocatalytic water decomposition reaction process, and provides a novel zirconium metal organic framework heterojunction material and a preparation method thereof, which effectively reduce the recombination probability of photo-generated electrons and holes, accelerate the surface water oxidation and reduction reaction kinetics and improve the photocatalytic water decomposition hydrogen production performance. The material has good chemical stability, and the preparation method is simple and can realize large-scale application.
In order to solve the technical problems, the invention is realized by the following technical scheme:
A Zr-metal-organic frame heterojunction material with photocatalytic performance comprises a Pt nanoparticle material and a Pt nanoparticle-coated NH2-UiO-66 material (Pt @ NH)2-UiO-66), preparation of outer layer deposited MnOxPt @ NH of nanolayers2-UiO-66 material (Pt @ NH)2-UiO-66@MnOx) Three steps;
The NH2-UiO-66 material size about 30-80 nm;
the Pt @ NH2-UiO-66@MnOxThe size of Pt nano particles in the material is 2-5 nm;
The Pt @ NH2-UiO-66@MnOxMnO in the materialxThe thickness of the nano layer is 5-20 nm.
A preparation method of a zirconium metal organic framework heterojunction material with photocatalytic performance comprises the following steps:
(1) Mixing 30-80mg of H2PtCl6·6H2O and 100-4Adding 00mg of polyvinylpyrrolidone (PVP) powder into 20mL of glycol solution, stirring in a water bath at 180 ℃ for 5-20 minutes, and centrifugally cleaning the obtained solution by using acetone and n-hexane to obtain a Pt solution with the concentration of 0.5-1.5 mg/mL;
(2) 5-20mg of ZrCl4And 10-20mg of 2-amino-1, 4-terephthalic acid (NH)2-BDC) is added into 5mL of N, N-Dimethylformamide (DMF), and after uniform mixing and stirring, 1.2mL of acetic acid and 0.2-1.0mL of Pt solution are added for hydrothermal synthesis. The resulting solution was centrifuged and washed with DMF and dried under vacuum at 60 ℃ for 12 hours to give light gray Pt @ NH2-UiO-66 powder;
(3) Adding 5-20mg of Pt @ NH2-UiO-66 powder was added to 0.066mM MnSO4And (4) uniformly stirring in the solution. After 10 minutes to 2 hours of irradiation with visible light, centrifugal drying is carried out. Roasting for 1-3h at 200 ℃ in air atmosphere to obtain light gray Pt @ NH2-UiO-66@MnOxAnd (3) powder.
The molecular weight of the polyvinylpyrrolidone (PVP) powder in the step (1) is 55000 +/-5000.
The grain diameter of the Pt nano particles in the Pt solution in the step (1) is 2-5 nm.
The hydrothermal synthesis condition in the step (2) is reaction synthesis for 6-24 hours at 100-150 ℃.
And (4) the visible light irradiation condition in the step (3) is that a 300W xenon lamp is matched with an optical filter with the wavelength of more than 420 nm.
The reaction time of the visible light irradiation in the step (3) is 10 minutes to 2 hours.
The invention has the beneficial effects that:
The main body of the zirconium metal organic framework heterojunction material is NH with octahedral nano morphology2Compared with the traditional inorganic metal oxide semiconductor material, the specific surface area of the-UiO-66 material is greatly increased, the contact area of the photocatalyst and the solution and the light absorption amount are greatly increased, the electron transfer to the interface of the material (solid or liquid-solid) can be effectively promoted, and the utilization rate of the material is improved.
The zirconium metal organic framework heterojunction material simultaneously loads reduction type cocatalyst Pt nano particles and oxidation type cocatalystMnO as agentxAnd separating them in the spatial dimension, at NH2The inside and the outside of the UiO-66 are respectively subjected to water reduction hydrogen production reaction and water oxidation oxygen production reaction, so that the possibility of electron and hole recombination is effectively reduced; meanwhile, reduction type cocatalyst Pt nano particles and oxidation type cocatalyst MnOxThe activation energy of the surface reduction and oxidation reaction can be obviously reduced, and the surface reaction rate is accelerated.
Compared with the traditional inorganic metal oxide semiconductor photocatalyst, the zirconium metal organic framework heterojunction material provided by the invention provides a novel morphology synthesis concept, provides a new thought for rational design of the photocatalyst, and makes a contribution to development of a photocatalytic semiconductor material with simple production process and high light energy conversion efficiency.
The preparation method of the zirconium metal organic framework heterojunction material is simple in operation process, does not need large-scale instruments and equipment, and is economical and feasible; meanwhile, the preparation process has strong controllability and excellent photocatalytic hydrogen production performance.
The zirconium metal organic framework heterojunction material can be used as an efficient photocatalytic water decomposition hydrogen production material, can be particularly used for producing hydrogen by photocatalytic reduction of water molecules, can efficiently convert solar energy into clean energy, and effectively relieves the current situations of shortage of fossil fuels, serious environmental pollution and the like.
Drawings
FIG. 1 is a transmission electron microscope photograph of Pt nanoparticles of example 1, with a 20nm scale;
FIG. 2 is Pt @ NH in example 12-transmission electron microscopy of UiO-66 at 100 nm;
FIG. 3 is Pt @ NH in example 12-UiO-66@MnOxTransmission electron microscopy of (5), scale 50 nm;
FIG. 4 is Pt @ NH in example 12-UiO-66@MnOxX-ray diffraction patterns of (a);
FIG. 5 is Pt @ NH in example 12-UiO-66@MnOxA fluorescence spectrum of (a);
FIG. 6 is a graph of Pt @ NH prepared in example 1 under simulated solar irradiation2-UiO-66@MnOxThe photocatalytic hydrogen production performance diagram.
Detailed Description
The present invention is further described in detail below by way of specific examples, which will enable one skilled in the art to more fully understand the present invention, but which are not intended to limit the invention in any way.
Example 1:
(1) Preparation of Pt nanoparticles
50.75mg of H2PtCl6·6H2O and 222mg of polyvinylpyrrolidone (PVP) powder are added into 20mL of glycol solution, stirred in a water bath at 180 ℃ for 10 minutes, and the obtained solution is centrifugally cleaned by acetone and n-hexane to prepare a solution with the concentration of 1.0 mg/mLPt.
(2)Pt@NH2Preparation of (E) -UiO-66
10.2mg of ZrCl4And 14.5mg of 2-amino-1, 4-terephthalic acid (NH)2-BDC) was added to 5mL of N, N-Dimethylformamide (DMF), and the mixture was stirred, followed by addition of 1.2mL of acetic acid and 0.5mL of the Pt solution obtained in step (1) of this example, and hydrothermal synthesis was carried out at 150 ℃ for 12 hours. The resulting solution was centrifuged and washed with DMF and dried under vacuum at 60 ℃ for 12 hours to give light gray Pt @ NH2-UiO-66 powder.
(3)Pt@NH2-UiO-66@MnOxPreparation of
10mg of Pt @ NH obtained in step (2) of this example2-UiO-66 powder was added to 0.066mM MnSO4And (4) uniformly stirring in the solution. After 1 hour of irradiation with visible light, the mixture was centrifuged and dried. Roasting for 2h at 200 ℃ in an air atmosphere to obtain light gray Pt @ NH2-UiO-66@MnOxAnd (3) powder.
fig. 1 is a transmission electron microscope image of Pt nanoparticles prepared in example 1. As shown in the transmission electron micrograph, the Pt nanoparticles are relatively uniform in size, about 3 nm.
FIG. 2 is Pt @ NH in example 12Transmission electron microscopy of UiO-66. As shown, each NH2the-UiO-66 material is good for wrapping Pt nano particles. Pt @ NH2the-UiO-66 size is about 50 nm.
FIG. 3 is Pt @ NH in example 12-UiO-66@MnOxTransmission electron microscopy images of (a). As shown, the photo-deposition process is at Pt @ NH2-UiO-66 carried on its surface a layer of amorphous MnOxLayer, thickness about 8 nm. The overall material size increased to 70 nm.
FIG. 4 is Pt @ NH in example 12-UiO-66@MnOxAnd the X-ray diffraction pattern of the related material. It can be observed that MnO was added with the coating of Pt particlesxDeposition of a layer, Pt @ NH2-UiO-66@MnOxRetains the original NH2-UiO-66 material characteristic peak. But due to Pt and MnOxIs small and the corresponding feature is not detected.
Table 1 shows Pt @ NH in example 12-UiO-66@MnOxAnd inductively coupled plasma emission spectrometer data of related materials. The material is proved to be loaded with trace Pt element and Mn element.
TABLE 1
FIG. 5 is Pt @ NH in example 12-UiO-66@MnOxand fluorescence spectra of the related materials. As can be seen from the figure, the Pt nanoparticles supporting the reducing promoter and the MnO of the oxidizing promoterxthen, Pt @ NH2-UiO-66@MnOxThe material has the weakest fluorescence intensity. This indicates that the material has a minimum degree of electron-hole recombination.
(4)Pt@NH2-UiO-66@MnOxIs used for preparing hydrogen by photocatalytic water decomposition.
Reacting NH2-UiO-66、Pt@NH2-UiO-66、NH2-UiO-66@MnOxAnd Pt @ NH2-UiO-66@MnOx10mg of each of the four samples was added to a sacrificial agent (acetonitrile: triethanolamine: water: 18: 2: 0.2) and stirred by ultrasound. Simulated ultraviolet light is obtained by using a 300W xenon lamp and a UV365 filter, the Pofely Labsolar-6A full-glass automatic online micro-gas analysis system uses argon as carrier gas, and the photocatalytic hydrogen production performance of the material is tested onlineCan be used.
FIG. 6 is a graph of Pt @ NH prepared in example 1 under simulated solar irradiation2-UiO-66@MnOxAnd a photocatalytic hydrogen production performance diagram of related materials. Compared with NH2-UiO-66、Pt@NH2-UiO-66 and NH2-UiO-66@MnOxThree materials, Pt @ NH2-UiO-66@MnOxThe photocatalytic hydrogen production performance is optimal and can reach 1451 mu mol g-1h-1。
Example 2:
(1) Preparation of Pt nanoparticles
The same as in example 1.
(2)Pt@NH2Preparation of (E) -UiO-66
10.2mg of ZrCl4And 14.5mg of 2-amino-1, 4-terephthalic acid (NH)2-BDC) was added to 5mL of N, N-Dimethylformamide (DMF), and the mixture was stirred, followed by addition of 1.2mL of acetic acid and 0.2mL of the Pt solution obtained in step (1) of this example, and hydrothermal synthesis was carried out at 150 ℃ for 12 hours. The resulting solution was centrifuged and washed with DMF and dried under vacuum at 60 ℃ for 12 hours to give light gray Pt @ NH2-UiO-66 powder.
(3)Pt@NH2-UiO-66@MnOxPreparation of
The same as in example 1.
The Pt nanoparticles are relatively uniform in size, about 3 nm. Each NH2the-UiO-66 material is good for wrapping Pt nano particles. But each one NH2The number of Pt particles wrapped by the-uo-66 material was much less than the sample of example 1. Pt @ NH2the-UiO-66 size is about 50 nm. After photo-deposition, Pt @ NH2The surface of the-UiO-66 is covered with a layer of amorphous MnOxLayer, thickness about 8 nm. The overall material size increased to 70 nm.
(4)Pt@NH2-UiO-66@MnOxFor preparing hydrogen by photocatalytic water decomposition
The Pt @ NH obtained in step (3) of this example2-UiO-66@MnOx10mg of the sample is taken and added into a sacrificial agent (acetonitrile: triethanolamine: water: 18: 2: 0.2) to be stirred evenly by ultrasound. Simulated ultraviolet light is obtained by using a 300W xenon lamp and a UV365 filter, and Pofely Labsolar-6A full-glass automatic onlineAnd in a trace gas analysis system, argon is used as carrier gas, and the photocatalytic hydrogen production performance of the material is tested on line.
Pt @ NH prepared in this example2-UiO-66@MnOxThe photocatalytic hydrogen production performance is about 1200 mu mol g-1h-1。
Example 3:
(1) preparation of Pt nanoparticles
The same as in example 1.
(2)Pt@NH2Preparation of (E) -UiO-66
10.2mg of ZrCl4And 14.5mg of 2-amino-1, 4-terephthalic acid (NH)2-BDC) was added to 5mL of N, N-Dimethylformamide (DMF), and the mixture was stirred, followed by addition of 1.2mL of acetic acid and 1.0mL of the Pt solution obtained in step (1) of this example, and hydrothermal synthesis was carried out at 150 ℃ for 12 hours. The resulting solution was centrifuged and washed with DMF and dried under vacuum at 60 ℃ for 12 hours to give light gray Pt @ NH2-UiO-66 powder.
(3)Pt@NH2-UiO-66@MnOxPreparation of
The same as in example 1.
The Pt nanoparticles are relatively uniform in size, about 3 nm. Each NH2the-UiO-66 material is good for wrapping Pt nano particles. But each one NH2The number of Pt particles wrapped by the-uo-66 material was much greater than that of the sample of example 1. Pt @ NH2the-UiO-66 size is about 50 nm. After photo-deposition, Pt @ NH2The surface of the-UiO-66 is covered with a layer of amorphous MnOxLayer, thickness about 8 nm. The overall material size increased to 70 nm.
(4)Pt@NH2-UiO-66@MnOxFor preparing hydrogen by photocatalytic water decomposition
The Pt @ NH obtained in step (3) of this example2-UiO-66@MnOx10mg of the sample is taken and added into a sacrificial agent (acetonitrile: triethanolamine: water: 18: 2: 0.2) to be stirred evenly by ultrasound. A300W xenon lamp is matched with a UV365 optical filter to obtain simulated ultraviolet light, the Pofely Labsolar-6A full-glass automatic online micro gas analysis system takes argon as carrier gas, and the photocatalytic hydrogen production performance of the material is tested online.
pt @ NH prepared in this example2-UiO-66@MnOxThe photocatalytic hydrogen production performance is about 965 mu mol g-1h-1。
Example 4:
(1) Preparation of Pt nanoparticles
The same as in example 1.
(2)Pt@NH2Preparation of (E) -UiO-66
The same as in example 1.
(3)Pt@NH2-UiO-66@MnOxPreparation of
10mg of Pt @ NH obtained in step (2) of this example2-UiO-66 powder was added to 0.066mM MnSO4And (4) uniformly stirring in the solution. After 10 minutes of irradiation with visible light, the mixture was centrifuged and dried. Roasting for 2h at 200 ℃ in an air atmosphere to obtain light gray Pt @ NH2-UiO-66@MnOxAnd (3) powder.
The Pt nanoparticles are relatively uniform in size, about 3 nm. Each NH2the-UiO-66 material is good for wrapping Pt nano particles. Pt @ NH2the-UiO-66 size is about 50 nm. After photo-deposition, Pt @ NH2The surface of the-UiO-66 is covered with a layer of amorphous MnOxLayer with a thickness of about 5 nm. The overall material size increased to about 60 nm.
(4)Pt@NH2-UiO-66@MnOxFor preparing hydrogen by photocatalytic water decomposition
The Pt @ NH obtained in step (3) of this example2-UiO-66@MnOx10mg of the sample is taken and added into a sacrificial agent (acetonitrile: triethanolamine: water: 18: 2: 0.2) to be stirred evenly by ultrasound. A300W xenon lamp is matched with a UV365 optical filter to obtain simulated ultraviolet light, the Pofely Labsolar-6A full-glass automatic online micro gas analysis system takes argon as carrier gas, and the photocatalytic hydrogen production performance of the material is tested online.
Pt @ NH prepared in this example2-UiO-66@MnOxThe photocatalytic hydrogen production performance is about 1149 mu mol g-1h-1。
Example 5:
(1) Preparation of Pt nanoparticles
The same as in example 1.
(2)Pt@NH2-UiO-66 preparation of
The same as in example 1.
(3)Pt@NH2-UiO-66@MnOxPreparation of
10mg of Pt @ NH obtained in step (2) of this example2-UiO-66 powder was added to 0.066mM MnSO4And (4) uniformly stirring in the solution. After 2 hours of irradiation with visible light, the mixture was centrifuged and dried. Roasting for 2h at 200 ℃ in an air atmosphere to obtain light gray Pt @ NH2-UiO-66@MnOxAnd (3) powder.
the Pt nanoparticles are relatively uniform in size, about 3 nm. Each NH2the-UiO-66 material is good for wrapping Pt nano particles. Pt @ NH2the-UiO-66 size is about 50 nm. After photo-deposition, Pt @ NH2The surface of the-UiO-66 is covered with a layer of amorphous MnOxLayer with a thickness of about 20 nm. The overall material size increased to about 90 nm.
(4)Pt@NH2-UiO-66@MnOxFor preparing hydrogen by photocatalytic water decomposition
The Pt @ NH obtained in step (3) of this example2-UiO-66@MnOx10mg of the sample is taken and added into a sacrificial agent (acetonitrile: triethanolamine: water: 18: 2: 0.2) to be stirred evenly by ultrasound. A300W xenon lamp is matched with a UV365 optical filter to obtain simulated ultraviolet light, the Pofely Labsolar-6A full-glass automatic online micro gas analysis system takes argon as carrier gas, and the photocatalytic hydrogen production performance of the material is tested online.
Pt @ NH prepared in this example2-UiO-66@MnOxThe photocatalytic hydrogen production performance is about 730 mu mol g-1h-1。
Example 6:
(1) Preparation of Pt nanoparticles
30mg of H2PtCl6·6H2O and 100mg of polyvinylpyrrolidone (PVP) powder are added into 20mL of glycol solution, stirred in a water bath at 180 ℃ for 5 minutes, and the obtained solution is centrifugally cleaned by acetone and n-hexane to prepare a solution with the concentration of 0.5 mg/mLPt.
(2)Pt@NH2preparation of (E) -UiO-66
5mg of ZrCl4And 10mg of 2-amino-1, 4-terephthalic acid(NH2-BDC) was added to 5mL of N, N-Dimethylformamide (DMF), and the mixture was stirred, and then 1.2mL of acetic acid and 0.5mL of the Pt solution obtained in the step (1) of this example were added to conduct hydrothermal synthesis at 120 ℃ for 6 hours. The resulting solution was centrifuged and washed with DMF and dried under vacuum at 60 ℃ for 12 hours to give light gray Pt @ NH2-UiO-66 powder.
(3)Pt@NH2-UiO-66@MnOxPreparation of
5mg of Pt @ NH obtained in step (2) of this example2-UiO-66 powder was added to 0.066mM MnSO4And (4) uniformly stirring in the solution. After 1 hour of irradiation with visible light, the mixture was centrifuged and dried. Roasting at 200 deg.c in air atmosphere for 1 hr to obtain light grey Pt @ NH2-UiO-66@MnOxAnd (3) powder.
The prepared Pt nano particles are uniform in size and about 2 nm. Each NH2the-UiO-66 material is good for wrapping Pt nano particles. Pt @ NH2the-UiO-66 size is about 30 nm. Photo-deposition method on Pt @ NH2-UiO-66 carried on its surface a layer of amorphous MnOxLayer, thickness about 8 nm. The overall material size is about 50 nm.
(4)Pt@NH2-UiO-66@MnOxFor preparing hydrogen by photocatalytic water decomposition
The Pt @ NH obtained in step (3) of this example2-UiO-66@MnOx10mg of the sample is taken and added into a sacrificial agent (acetonitrile: triethanolamine: water: 18: 2: 0.2) to be stirred evenly by ultrasound. A300W xenon lamp is matched with a UV365 optical filter to obtain simulated ultraviolet light, the Pofely Labsolar-6A full-glass automatic online micro gas analysis system takes argon as carrier gas, and the photocatalytic hydrogen production performance of the material is tested online.
Pt @ NH prepared in this example2-UiO-66@MnOxThe photocatalytic hydrogen production performance is about 1066 mu mol g-1h-1。
Example 7:
(1) Preparation of Pt nanoparticles
80mg of H2PtCl6·6H2O and 400mg polyvinylpyrrolidone (PVP) powder were added to 20mL of ethylene glycol solution, and stirred in a water bath at 180 ℃ for 20 minutes to obtainThe solution was centrifugally washed with acetone and n-hexane to prepare a Pt solution with a concentration of 1.0 mg/mL.
(2)Pt@NH2preparation of (E) -UiO-66
20mg of ZrCl4And 20mg of 2-amino-1, 4-terephthalic acid (NH)2BDC) was added to 5mL of Dimethylformamide (DMF), and after stirring and mixing, 1.2mL of acetic acid and 0.5mL of the Pt solution obtained in step (1) of this example were added to conduct hydrothermal synthesis at 180 ℃ for 24 hours. The resulting solution was centrifuged and washed with DMF and dried under vacuum at 60 ℃ for 12 hours to give light gray Pt @ NH2-UiO-66 powder.
(3)Pt@NH2-UiO-66@MnOxPreparation of
20mg of Pt @ NH obtained in step (2) of this example2-UiO-66 powder was added to 0.066mM MnSO4And (4) uniformly stirring in the solution. After 1 hour of irradiation with visible light, the mixture was centrifuged and dried. Roasting for 3 hours at 200 ℃ in an air atmosphere to obtain light gray Pt @ NH2-UiO-66@MnOxAnd (3) powder.
The prepared Pt nano particles are uniform in size and about 5 nm. Each NH2the-UiO-66 material is good for wrapping Pt nano particles. Pt @ NH2the-UiO-66 size is about 80 nm. Photo-deposition method on Pt @ NH2-UiO-66 carried on its surface a layer of amorphous MnOxLayer, thickness about 8 nm. The overall material size is about 100 nm.
(4)Pt@NH2-UiO-66@MnOxFor preparing hydrogen by photocatalytic water decomposition
The Pt @ NH obtained in step (3) of this example2-UiO-66@MnOx10mg of the sample is taken and added into a sacrificial agent (acetonitrile: triethanolamine: water: 18: 2: 0.2) to be stirred evenly by ultrasound. A300W xenon lamp is matched with a UV365 optical filter to obtain simulated ultraviolet light, the Pofely Labsolar-6A full-glass automatic online micro gas analysis system takes argon as carrier gas, and the photocatalytic hydrogen production performance of the material is tested online.
Pt @ NH prepared in this example2-UiO-66@MnOxThe photocatalytic hydrogen production performance is about 700 mu mol g-1h-1。
In order to make the embodiments more clear and intuitive, table 2 is a summary table of indexes and parameters in the embodiments.
TABLE 2
Table 3 shows the ranges of the indexes in the examples of the present invention and the optimum values of the indexes in the present invention.
Index (I) Range of Optimum value
H2PtCl66H2O mass 30-80mg 50.75
Quality of PVP 100-400mg 222
Time of water bath 5-20 minutes 10
Quality of zirconium chloride 5-20mg 10.2
NH2-BDC mass 10-20mg 14.5
Volume of Pt solution 0.2-1.0mL 0.5
Hydrothermal temperature 120-180℃ 150
Time of water heating 6 to 24 hours 12
Pt@NH2-UiO-66 mass 5-20mg 10
Time of visible light irradiation 10 minutes to 2 hours 1 hour
Time of calcination 1-3 hours 2
TABLE 3
although the preferred embodiments of the present invention have been described with reference to the accompanying drawings, the present invention is not limited to the above-described embodiments, which are merely illustrative and not restrictive, and those skilled in the art can make various changes and modifications within the spirit and scope of the present invention without departing from the spirit and scope of the appended claims.

Claims (8)

1. a zirconium metal organic framework heterojunction material with photocatalytic properties comprising NH as host photocatalytic semiconductor MOF material2-UiO-66, including Pt nanoparticles encapsulated therein, and MnO deposited as a monolithic outer layerxNanolayer characterized by the NH2the-UiO-66 material is in a regular octahedral shape;
Wherein NH2-UiO-66 material size 30-80 nm;
Wherein Pt @ NH2-UiO-66@MnOxThe size of Pt nano particles in the material is 2-5 nm;
Wherein Pt @ NH2-UiO-66@MnOxMnO in the materialxThe thickness of the nano layer is 5-20 nm.
2. The Zr-MOF heterojunction material as claimed in claim 1, wherein the Pt nanoparticles as reduction promoter are completely coated in NH2-UiO-66 material interior.
3. The Zr-MOF heterojunction material as claimed in claim 1, wherein said MnO is MnOxThe nano layer is used as an oxidation type cocatalyst and uniformly covers NH2-UiO-66 material exterior.
4. A method for preparing a zirconium metal organic framework heterojunction material with photocatalytic properties according to any of claims 1 to 3, characterized in that it is carried out according to the following steps:
(1) Mixing 30-80mg of H2PtCl6·6H2Adding O and 100-400mg polyvinylpyrrolidone (PVP) powder into 20mL of glycol solution, stirring in water bath at 180 ℃ for 5-20 minutes, and centrifugally cleaning the obtained solution by acetone and n-hexane to obtain a Pt solution with the concentration of 0.5-1.5 mg/mL;
(2) 5-20mg of ZrCl4And 10-20mg of 2-amino-1, 4-terephthalic acid (NH)2-BDC) is added into 5mL of N, N-Dimethylformamide (DMF), and after being mixed and stirred evenly, 1.2mL of acetic acid and 0.2-1.0mL of Pt solution are added for hydrothermal synthesis, the obtained solution is centrifugally cleaned by DMF, and is dried for 12 hours in vacuum at 60 ℃ to obtain light gray Pt @ NH2-UiO-66 powder;
(3) Adding 5-20mg of Pt @ NH2-UiO-66 powder was added to 0.066mM MnSO4Uniformly stirring in the solution, irradiating for 10 min-2 hr with visible light, centrifuging, drying, and calcining at 200 deg.C in air atmosphere for 1-3 hr to obtain light gray Pt @ NH2-UiO-66@MnOxAnd (3) powder.
5. The method for preparing a zirconium metal organic framework heterojunction material with photocatalytic performance as claimed in claim 4, wherein the molecular weight of the polyvinylpyrrolidone (PVP) powder in step (1) is 55000 ± 5000.
6. The method for preparing a Zr-MOF heterojunction material with photocatalytic performance as claimed in claim 4, wherein the Pt nanoparticles in the Pt solution in step (1) have a particle size of 2-5 nm.
7. The method for preparing a Zr-MOF heterojunction material with photocatalytic performance as claimed in claim 4, wherein the hydrothermal synthesis conditions in step (2) are 100-180 ℃ for 6-24 hours.
8. The method for preparing a Zr-MOF heterojunction material as claimed in claim 4, wherein the irradiation condition of visible light in step (3) is 300W xenon lamp with filter with wavelength >420 nm.
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