Preparation method of substrate of fixed photocatalyst and fixed photocatalyst

Abstract

The invention relates to the technical field of photocatalysts, in particular to a preparation method of a substrate of a fixed photocatalyst and the fixed photocatalyst. Wherein the target substrate is provided with the surface microstructure array, so that the contact area of the photocatalyst and the aqueous solution can be effectively increased, meanwhile, the target mixed solution mixed with the photocatalyst material can be coated on the substrate, and the coating obtained by drying can ensure that the coating has better stability in the aqueous solution; in addition, the array substrate with the surface microstructure is prepared by adopting a 3D printing method, so that the specific surface area of the photocatalyst can be enlarged, the contact area with a reaction medium is increased, and the photocatalytic efficiency is improved.

Description

Technical Field

[0001] The present invention relates to the technical field of photocatalysts, and in particular to a method for preparing a substrate of a fixed photocatalyst and the fixed photocatalyst. Background Art

[0002] In the related art, a common method for photocatalytic hydrogen experiments is to suspend powdered photocatalysts in aqueous solution. However, the photocatalytic efficiency of this method is low. Summary of the invention

[0003] The embodiments of the present invention provide a method for preparing a substrate of a fixed photocatalyst and a fixed photocatalyst, which can improve the photocatalytic efficiency.

[0004] In a first aspect, an embodiment of the present invention provides a method for preparing a substrate of a fixed photocatalyst, comprising:

[0005] Step S21, mixing and stirring hydroxyethyl methacrylate, tetraethylene glycol diacrylate, phenoxyethanol, and 2,2-dimethoxy-2-phenylacetophenone to obtain a light-curable ink;

[0006] Step S22, designing surface microstructure units on a modeling software, and arraying the surface microstructure units to obtain a substrate model;

[0007] Step S23, importing the substrate model into a photocurable 3D printer, using the photocurable ink to print out a substrate to be dried having a surface microstructure array, and placing the substrate to be dried in a vacuum drying oven for a first drying to obtain a target substrate; wherein the surface of the target substrate is used to fix the coating, and the coating is obtained by performing a second drying on a target mixed solution containing a photocatalyst material.

[0008] In a second aspect, an embodiment of the present invention provides a fixed photocatalyst, comprising a substrate and a coating fixed on the substrate, wherein the substrate is prepared by the method described in the above embodiment.

[0009] The embodiment of the present invention provides a method for preparing a substrate of a fixed photocatalyst and a fixed photocatalyst. Since the target substrate has a surface microstructure array, the contact area between the photocatalyst and the aqueous solution can be effectively increased. At the same time, the target mixed solution containing the photocatalyst material can be coated on the substrate. The coating obtained by drying can ensure good stability in the aqueous solution. In addition, the 3D printing method is used to prepare a substrate with a surface microstructure array, which can expand the specific surface area of ​​the photocatalyst, increase the contact area with the reaction medium, and improve the photocatalytic efficiency. BRIEF DESCRIPTION OF THE DRAWINGS

[0010] In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings required for use in the embodiments or the description of the prior art will be briefly introduced below. Obviously, the drawings described below are some embodiments of the present invention. For ordinary technicians in this field, other drawings can be obtained based on these drawings without paying creative work.

[0011] Figure 1 is a flow chart of a method for preparing a substrate of a fixed photocatalyst provided in an embodiment of the present invention;

[0012] Figure 2 is a physical picture of a substrate in a fixed photocatalyst provided in an embodiment of the present invention;

[0013] Figure 3 yes Figure 2 SEM images of the substrate shown. DETAILED DESCRIPTION

[0014] In order to make the purpose, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below in conjunction with the drawings in the embodiments of the present invention. Obviously, the described embodiments are part of the embodiments of the present invention, rather than all the embodiments. Based on the embodiments in the present invention, all other embodiments obtained by ordinary technicians in this field without making creative work are within the scope of protection of the present invention.

[0015] Please refer to Figure 1 The embodiment of the present invention provides a method for preparing a substrate of a fixed photocatalyst, comprising:

[0016] Step S21, mixing and stirring hydroxyethyl methacrylate, tetraethylene glycol diacrylate, phenoxyethanol, and 2,2-dimethoxy-2-phenylacetophenone to obtain a light-curable ink;

[0017] Step S22, designing surface microstructure units on a modeling software, and arraying the surface microstructure units to obtain a substrate model;

[0018] Step S23, importing the substrate model into a photocurable 3D printer, using photocurable ink to print out a substrate to be dried with a surface microstructure array, and placing the substrate to be dried in a vacuum drying oven for a first drying to obtain a target substrate; wherein the surface of the target substrate is used to fix the coating, and the coating is obtained by second drying a target mixed solution containing a photocatalyst material.

[0019] In this embodiment, since the target substrate has a surface microstructure array, the contact area between the photocatalyst and the aqueous solution can be effectively increased. At the same time, the target mixed solution containing the photocatalyst material can be coated on the substrate. The coating obtained by drying can ensure good stability in the aqueous solution. In addition, the 3D printing method is used to prepare a substrate with a surface microstructure array, which can expand the specific surface area of ​​the photocatalyst, increase the contact area with the reaction medium, and improve the photocatalytic efficiency.

[0020] In one embodiment of the present invention, in step S21, the volume ratio of hydroxyethyl methacrylate, tetraethylene glycol diacrylate and phenoxyethanol is 3-4:1-1.8:1.

[0021] In one embodiment of the present invention, in step S21, the amount of 2,2-dimethoxy-2-phenylacetophenone added is 0.1-0.25 mol / L.

[0022] In one embodiment of the present invention, in step S21, the stirring temperature is 15-35°C, the time is 0.5-2h, and the rotation speed is 800-1500r / min.

[0023] In one embodiment of the present invention, in step S22, the modeling software includes Solidworks and Pro / E, and the modeling file format is .stl file.

[0024] See also Figure 2 and Figure 3 In one embodiment of the present invention, in step S22, the shape of the surface microstructure unit includes a convex pyramid, a concave pyramid, a convex hemisphere, a concave hemisphere, a convex cylinder and a concave cylinder. That is, the outer convexity can be a convex pyramid (where Figure 2 The outer convex pyramid is shown), a convex hemisphere or a convex cylinder, and the inner concave pyramid can be a concave pyramid (where Figure 2 The ones shown are concave pyramids), concave hemispheres or concave cylinders; the flat plate is an ordinary substrate without any surface microstructure treatment. Figure 2 It can be seen that by setting the surface microstructure unit, the specific surface area of ​​the substrate can be increased. Moreover, considering that the 3D printing process is interlayer printing, each layer has steps, so this can also increase the specific surface area of ​​the substrate to a certain extent. Figure 3 Shown from top to bottom are convex, concave and flat, and the coating thicknesses are 55.24μm, 252.3μm and 22.42μm respectively. It can be seen that the substrate with a concave configuration can attach more photocatalysts, that is, the photocatalytic efficiency of this type of substrate is the highest, followed by the substrate with a convex configuration, and finally the substrate with a flat configuration.

[0025] In one embodiment of the present invention, in step S22, the arrayed arrangement includes a rectangular array, a triangular array, a hexagonal array and a circular array.

[0026] In one embodiment of the present invention, in step S23, the wavelength of the light source of the light-curing 3D printer is 385 nm, and the printing time is 3 hours.

[0027] In one embodiment of the present invention, in step S23, the first drying temperature is 70-90° C., the time is 10-12 hours, and the second drying temperature is 100-120° C., the time is 1-2 hours.

[0028] In addition, an embodiment of the present invention further provides a fixed photocatalyst, including a substrate and a coating fixed on the substrate, and the substrate is prepared by the method mentioned in any of the above embodiments.

[0029] In the related art, methods for depositing photocatalysts on substrates mainly include hydrothermal reaction and melting, however, these methods have low preparation efficiency.

[0030] In order to solve this technical problem, it is possible to consider improving the coating.

[0031] In one embodiment of the present invention, the fixed photocatalyst coating can be prepared by the following method:

[0032] Step S11, adding ZnCl2, InCl3·4H2O and glycerol to deionized water and stirring until the solution is clear, then adding thioacetamide and stirring until the solution is clear, to obtain a first mixed solution;

[0033] Step S12, placing the first mixed solution in a hydrothermal reactor for hydrothermal reaction, cooling to room temperature after the reaction is completed, and washing and drying the collected reaction product to obtain an intermediate reaction product;

[0034] Step S13, dispersing the intermediate reaction product in an aqueous solution containing H2PtCl6·6H2O and Co(NO3)2, and then continuously irradiating the solution with a light source, keeping the solution continuously stirred during the irradiation, and washing and drying the collected reaction product to obtain a ZnIn2S4-Pt-Co nanosphere photocatalyst;

[0035] Step S14, adding ethylene glycol and the obtained ZnIn2S4-Pt-Co nanosphere photocatalyst into deionized water and stirring, then adding hydroxyethyl methacrylate, and continuously irradiating the solution with a light source, and keeping the solution continuously stirred during the irradiation period, to obtain a second mixed solution;

[0036] Step S15, adding anhydrous citric acid to the second mixed solution and stirring until completely dissolved to obtain a target mixed solution containing ZnIn2S4-Pt-Co nanosphere photocatalyst;

[0037] Step S16, coating the target mixed solution on the substrate and drying it to obtain a fixed photocatalyst coating; wherein the fixed photocatalyst includes a substrate and a coating fixed on the substrate.

[0038] In this embodiment, during the hydrothermal reaction, Zn 2+ 、In 3+ The ZnIn2S4 nuclei are formed with the hydrolyzed thioacetamide, and then the ZnIn2S4 nuclei are continuously produced, and a petal-shaped surface structure is generated according to the crystal orientation, so that it has a higher specific surface area and becomes a porous nanosphere material; the Pt and Co elements are anchored on the porous ZnIn2S4 surface to form stable active sites. Therefore, by loading highly active Pt and Co catalysts through the ZnIn2S4-Pt-Co flower-shaped nanosphere structure, the specific surface area and active sites of the catalyst can be effectively increased, and the amount of precious metal catalyst can also be effectively reduced. At the same time, the prepared fixed photocatalyst coating can be coated on plastic, metal and other substrates, and has excellent stability in aqueous solution, and can be used as a reaction substrate in photocatalytic hydrogen and oxygen evolution reactions.

[0039] As a member of metal chalcogenides, ternary sulfide ZnIn2S4 has attracted extensive attention due to its chemical and optical stability, appropriate band gap (2.3-2.6 eV) and non-toxicity. However, the low photoactivity of ZnIn2S4 due to heavy carrier recombination remains a challenge. Co-catalysts supported on photocatalysts, including noble metals (such as Rh, Pd), can serve as reaction sites and carrier capture sites, thereby promoting the directional migration of charges with the help of strong electronic interactions at the interface and improving the rate of photocatalytic hydrogen evolution.

[0040] In one embodiment of the present invention, in step S11, the molar ratio of thioacetamide, InCl3·4H2O and ZnCl2 is 8-15:2-2.5:1, and the volume ratio of deionized water and glycerol is 10-15:1.

[0041] In one embodiment of the present invention, in step S12, the temperature of the hydrothermal reaction is 160-200° C., the time is 24-36 hours, and the pressure is 3-8 MPa.

[0042] In one embodiment of the present invention, the drying temperature is 70-90° C. and the drying time is 10-12 hours.

[0043] In one embodiment of the present invention, the ratio of the added amounts of H2PtCl6·6H2O and Co(NO3)2 is 1:1.

[0044] In one embodiment of the present invention, the drying temperature is 70-90° C. and the drying time is 10-12 hours.

[0045] In one embodiment of the present invention, in step S14, the volume ratio of deionized water to ethylene glycol is 1-1.5:1, and the amount of hydroxyethyl methacrylate added is 1-2.5 mmol / ml.

[0046] In one embodiment of the present invention, in step S15, the amount of anhydrous citric acid added is 1-2 μmol / ml.

[0047] In one embodiment of the present invention, in step S16, the drying temperature is 100-120° C. and the drying time is 1-2 hours.

[0048] It should be noted that the purpose of steps S14 to S16 is to prepare a target mixed solution containing ZnIn2S4-Pt-Co nanosphere photocatalyst, and further obtain a coating fixed on the substrate, thereby improving the preparation efficiency of the photocatalyst.

[0049] It should be noted that, in this article, relational terms such as first and second are only used to distinguish one entity or operation from another entity or operation, and do not necessarily require or imply any such actual relationship or order between these entities or operations. Moreover, the terms "include", "comprise" or any other variants thereof are intended to cover non-exclusive inclusion, so that a process, method, article or device including a series of elements includes not only those elements, but also other elements not explicitly listed, or also includes elements inherent to such process, method, article or device.

[0050] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention, rather than to limit it. Although the present invention has been described in detail with reference to the aforementioned embodiments, those skilled in the art should understand that they can still modify the technical solutions described in the aforementioned embodiments, or make equivalent replacements for some of the technical features therein. However, these modifications or replacements do not deviate the essence of the corresponding technical solutions from the spirit and scope of the technical solutions of the embodiments of the present invention.

Claims

1. A method for preparing a substrate of a fixed photocatalyst, characterized in that: include: Step S21, mixing and stirring hydroxyethyl methacrylate, tetraethylene glycol diacrylate, phenoxyethanol, and 2,2-dimethoxy-2-phenylacetophenone to obtain a light-curable ink; Step S22, designing surface microstructure units on a modeling software, and arraying the surface microstructure units to obtain a substrate model; Step S23, importing the substrate model into a photocurable 3D printer, using the photocurable ink to print out a substrate to be dried having a surface microstructure array, and placing the substrate to be dried in a vacuum drying oven for a first drying to obtain a target substrate; wherein the surface of the target substrate is used to fix the coating, and the coating is obtained by performing a second drying on a target mixed solution containing a photocatalyst material.

2. The method according to claim 1, characterized in that In step S21, the volume ratio of hydroxyethyl methacrylate, tetraethylene glycol diacrylate and phenoxyethanol is 3-4:1-1.8:

1.

3. The method according to claim 2, characterized in that In step S21, the amount of 2,2-dimethoxy-2-phenylacetophenone added is 0.1 to 0.25 mol / L.

4. The method according to claim 1, characterized in that: In step S21, the stirring temperature is 15-35°C, the time is 0.5-2h, and the rotation speed is 800-1500r / min.

5. The method according to claim 1, characterized in that In step S22, the modeling software includes Solidworks and Pro / E, and the modeling file format is .stl file.

6. The method according to claim 1, characterized in that In step S22, the shapes of the surface microstructure units include convex pyramids, concave pyramids, convex hemispheres, concave hemispheres, convex cylinders and concave cylinders.

7. The method according to claim 1, characterized in that In step S22, the arrayed arrangement includes a rectangular array, a triangular array, a hexagonal array and a circular array.

8. The method according to claim 1, characterized in that In step S23, the wavelength of the light source of the light-curing 3D printer is 385 nm, and the printing time is 3 hours.

9. The method according to any one of claims 1 to 8, characterized in that In step S23, the first drying temperature is 70-90°C for 10-12 hours, and the second drying temperature is 100-120°C for 1-2 hours.

10. A fixed photocatalyst, characterized in that: The invention comprises a substrate and a coating fixed on the substrate, wherein the substrate is prepared by the method according to any one of claims 1 to 9.

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