A method for preparing a substrate for a fixed photocatalyst and the fixed photocatalyst itself.

Abstract

This invention relates to the field of photocatalyst technology, and particularly to a method for preparing a substrate for a fixed photocatalyst and the fixed photocatalyst itself. The target substrate possesses a surface microstructure array, which effectively increases the contact area between the photocatalyst and the aqueous solution. Simultaneously, a target mixed solution containing photocatalyst materials can be coated onto the substrate, and the resulting coating, after drying, ensures good stability in the aqueous solution. Furthermore, using 3D printing to prepare the substrate with the surface microstructure array can expand the specific surface area of ​​the photocatalyst, increase the contact area with the reaction medium, and improve photocatalytic efficiency.

Description

Technical Field

[0001] This invention relates to the field of photocatalyst technology, and in particular to a method for preparing a substrate for a fixed photocatalyst and the fixed photocatalyst itself. Background Technology

[0002] In related technologies, a common method for photocatalytic hydrogen experiments is to suspend powdered photocatalysts in aqueous solutions; however, this method has low photocatalytic efficiency. Summary of the Invention

[0003] This invention provides a method for preparing a substrate for a fixed photocatalyst and a fixed photocatalyst, which can improve photocatalytic efficiency.

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

[0005] Step S21: Mix and stir hydroxyethyl methacrylate, tetraethylene glycol diacrylate, phenoxyethanol, and 2,2-dimethoxy-2-phenylacetophenone to obtain a photocurable ink;

[0006] Step S22: Design surface microstructure units on modeling software and array the surface microstructure units to obtain a substrate model;

[0007] Step S23: Import the substrate model into the photopolymer 3D printer, use the photopolymer ink to print a substrate with a surface microstructure array to be dried, and place the substrate to be dried in a vacuum drying oven for a first drying to obtain the target substrate; wherein, the surface of the target substrate is used to fix the coating, and the coating is obtained by a second drying of the target mixed solution containing photocatalyst material.

[0008] Secondly, embodiments of the present invention provide a fixed photocatalyst, comprising a substrate and a coating fixed on the substrate, wherein the substrate is prepared using the method described in the above embodiments.

[0009] This invention provides a method for preparing a substrate for 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 photocatalyst materials can be coated on the substrate, and the coating obtained by drying can ensure good stability in the aqueous solution. In addition, the substrate with a surface microstructure array is prepared by 3D printing, which can expand the specific surface area of ​​the photocatalyst, increase the contact area with the reaction medium, and improve the photocatalytic efficiency. Attached Figure Description

[0010] To more clearly illustrate the technical solutions in the embodiments of the present invention or the prior art, the drawings used in the description of the embodiments or the prior art will be briefly introduced below. Obviously, the drawings described below are some embodiments of the present invention. For those skilled in the art, other drawings can be obtained based on these drawings without creative effort.

[0011] Figure 1 This is a flowchart of the substrate preparation method for the immobilized photocatalyst provided in the embodiments of the present invention;

[0012] Figure 2 This is a physical image of the substrate in the immobilized photocatalyst provided in the embodiments of the present invention;

[0013] Figure 3 yes Figure 2 A schematic diagram of the SEM image of the substrate shown. Detailed Implementation

[0014] To make the objectives, technical solutions, and advantages of the embodiments of the present invention clearer, the technical solutions of the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings. Obviously, the described embodiments are some embodiments of the present invention, but not all embodiments. All other embodiments obtained by those skilled in the art based on the embodiments of the present invention without creative effort are within the scope of protection of the present invention.

[0015] Please refer to Figure 1 This invention provides a method for preparing a substrate for a fixed photocatalyst, comprising:

[0016] Step S21: Mix and stir hydroxyethyl methacrylate, tetraethylene glycol diacrylate, phenoxyethanol, and 2,2-dimethoxy-2-phenylacetophenone to obtain a photocurable ink;

[0017] Step S22: Design surface microstructure units in modeling software and array the surface microstructure units to obtain the substrate model;

[0018] Step S23: Import the substrate model into the photopolymer 3D printer, print the substrate with a surface microstructure array using photopolymer ink, and place the substrate to be dried in a vacuum drying oven for the first drying to obtain the target substrate; wherein, the surface of the target substrate is used to fix the coating, and the coating is obtained by the second drying of the target mixed solution containing 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 photocatalyst material can be coated on the substrate, and the coating obtained by drying can ensure good stability in the aqueous solution. In addition, the substrate with surface microstructure array is prepared by 3D printing, 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 to 0.25 mol / L.

[0022] In one embodiment of the present invention, in step S21, the stirring temperature is 15-35°C, the stirring time is 0.5-2 hours, and the stirring speed is 800-1500 r / 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] Please see 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 outward convexity can be a convex pyramid (wherein... Figure 2 The diagram shows an outwardly convex pyramid, a convex hemisphere, or a convex cylinder; the inwardly concave pyramid can be a concave pyramid (where...). Figure 2 The diagram shows concave pyramids, concave hemispheres, or concave cylinders; while the flat plate is a plain substrate without any surface microstructure treatment. Figure 2 It can be seen that by setting surface microstructure units, the specific surface area of ​​the substrate can be increased. Moreover, considering that 3D printing is an interlayer printing process, each layer has steps, which can also increase the specific surface area of ​​the substrate to a certain extent. Figure 3 The images shown, from top to bottom, are convex, concave, and flat, with coating thicknesses of 55.24 μm, 252.3 μm, and 22.42 μm, respectively. It can be seen that the concave substrate can attach more photocatalyst, meaning that this type of substrate has the highest photocatalytic efficiency, followed by the convex substrate, and finally the flat substrate.

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

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

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

[0028] Furthermore, embodiments of the present invention also provide a fixed photocatalyst, comprising a substrate and a coating fixed on the substrate, wherein the substrate is prepared using the method mentioned in any of the above embodiments.

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

[0030] To address this technical problem, improvements to the coating could be considered.

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

[0032] Step S11: Add ZnCl2, InCl3·4H2O and glycerol to deionized water and stir until clear. Then add thioacetamide and stir until clear to obtain the first mixed solution.

[0033] Step S12: Place the first mixed solution in a hydrothermal reactor for hydrothermal reaction. After the reaction is completed, cool it to room temperature and wash and dry the collected reaction product to obtain the intermediate reaction product.

[0034] Step S13: Disperse the intermediate reaction product in an aqueous solution containing H2PtCl6·6H2O and Co(NO3)2, then continuously irradiate it with a light source while keeping the solution continuously stirred during irradiation, and wash and dry the collected reaction product to obtain ZnIn2S4-Pt-Co nanosphere photocatalyst.

[0035] Step S14: Add ethylene glycol and the obtained ZnIn2S4-Pt-Co nanosphere photocatalyst to deionized water and stir. Then add hydroxyethyl methacrylate and continuously irradiate the solution with a light source. During the irradiation, keep the solution continuously stirred to obtain a second mixed solution.

[0036] Step S15: Add anhydrous citric acid to the second mixed solution and stir until completely dissolved to obtain the target mixed solution containing ZnIn2S4-Pt-Co nanosphere photocatalyst;

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

[0038] In this embodiment, during the hydrothermal reaction process, Zn 2+ In 3+ ZnIn2S4 crystal nuclei are formed by the hydrolysis of thioacetamide. These nuclei continue to grow, forming a petal-like surface structure according to crystal orientation, resulting in a high specific surface area and creating porous nanospheres. Pt and Co elements are anchored on the porous ZnIn2S4 surface, forming stable active sites. Therefore, loading highly active Pt and Co catalysts onto ZnIn2S4-Pt-Co flower-like nanospheres effectively increases the specific surface area and active sites of the catalyst, while also reducing the amount of precious metal catalyst required. Furthermore, the resulting immobilized photocatalyst coating can be applied to substrates such as plastics and metals, and exhibits excellent stability in aqueous solutions, making it suitable as a reaction substrate for photocatalytic hydrogen and oxygen evolution reactions.

[0039] As a member of the metal chalcogenides, the ternary sulfide ZnIn₂S₄ has attracted widespread attention due to its chemical and optical stability, suitable band gap (2.3-2.6 eV), and non-toxicity. However, its low photoactivity remains a challenge due to the recombination of heavily loaded charge carriers. Cocatalysts supported on photocatalysts, including noble metals (such as Rh and Pd), can serve as reaction sites and support trapping sites, thereby promoting the directional migration of charges through strong electronic interactions at the interface and improving the photocatalytic hydrogen evolution rate.

[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 amount of H2PtCl6·6H2O to the amount of Co(NO3)2 added 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 to 1.5:1, and the amount of hydroxyethyl methacrylate added is 1 to 2.5 mmol / ml.

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

[0047] In one embodiment of the present invention, in step S16, the drying temperature is 100-120°C and the 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 document, relational terms such as "first" and "second" are used only to distinguish one entity or operation from another, and do not necessarily require or imply any such actual relationship or order between these entities or operations. Furthermore, the terms "comprising," "including," or any other variations thereof are intended to cover non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements includes not only those elements but also other elements not expressly listed, or elements inherent to such a process, method, article, or apparatus.

[0050] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention, and not to limit them; although the present invention has been described in detail with reference to the foregoing embodiments, those skilled in the art should understand that modifications can still be made to the technical solutions described in the foregoing embodiments, or equivalent substitutions can be made to some of the technical features; and these modifications or substitutions do not cause the essence of the corresponding technical solutions to deviate from the spirit and scope of the technical solutions of the embodiments of the present invention.

Claims

1. A method for preparing a fixed photocatalyst substrate, characterized by, The method comprises the following steps: Step S21, mixing and stirring hydroxyethyl methacrylate, tetraethylene glycol diacrylate, phenoxyethanol and 2,2-dimethoxy-2-phenylacetophenone to obtain a photocuring ink; Step S22, designing a surface microstructure unit on a modeling software and arraying the surface microstructure unit to obtain a substrate model; wherein the shape of the surface microstructure unit comprises convex pyramids, concave pyramids, convex hemispheres, concave hemispheres, convex cylinders and concave cylinders; Step S23, importing the substrate model into a photocuring 3D printer, printing a to-be-dried substrate with a surface microstructure array by using the photocuring ink, and placing the to-be-dried substrate in a vacuum drying oven for first drying to obtain a target substrate; wherein the surface of the target substrate is used for fixing a coating, and the coating is obtained by second drying a target mixed solution containing a photocatalyst material.

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

1.

3. The method of claim 2, wherein, In step S21, the addition amount of 2,2-dimethoxy-2-phenylacetophenone is 0.1-0.25 mol / L.

4. The method of claim 1, wherein, In step S21, the stirring temperature is 15-35℃, the stirring time is 0.5-2h, and the stirring speed is 800-1500r / min.

5. The method of claim 1, wherein, In step S22, the modeling software comprises Solidworks and Pro / E, and the modeling file format is.stl file.

6. The method of claim 1, wherein, In step S22, the arraying arrangement comprises rectangular array, triangular array, hexagonal array and circular array.

7. The method of claim 1, wherein, In step S23, the wavelength of the light source of the photocuring 3D printer is 385nm, and the printing time is 3h.

8. The method according to any one of claims 1 to 7, characterized in that, In step S23, the first drying temperature is 70-90℃, the first drying time is 10-12h, the second drying temperature is 100-120℃, and the second drying time is 1-2h.

9. A fixed photocatalyst, characterized by The substrate and the coating fixed on the substrate are prepared by the method according to any one of claims 1-8.

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