Biomimetic vertical type 3D printing photocatalyst and preparation method and application thereof

Abstract

The present application relates to a kind of preparation method of bionic vertical type 3D printing photocatalyst and its application, the photocatalyst of the present application first introduces the concept of monolithic catalyst into the field of photocatalytic CO2 reduction, Al2O3 Array made by using stereolithography 3D printing technology is carrier and three-dimensional skeleton, CdIn2S4 is grown on array surface by hydrothermal method, so that the bionic vertical type 3D printing photocatalyst with three-dimensional structure is obtained, and the specific surface area of dense array is increased, which can provide abundant surface reaction sites for light-driven chemical reactions, thereby effectively solving the defects of the limited specific surface area of traditional catalyst;Meanwhile, the catalyst realizes high loading of active center in Z-axis direction, and has macro mass transfer channel, thereby effectively improving catalytic activity.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of photocatalysts, in particular to a biomimetic vertical 3D printed photocatalyst, and further relates to a preparation method and application of the photocatalyst. BACKGROUND

[0002] As one of the most promising green new technologies, photocatalytic technology can convert greenhouse gases such as carbon dioxide into high-value-added chemicals and fuels through solar energy, which is conducive to solving the problems of fossil fuel shortage and global environmental pollution. However, due to the fact that the photocatalytic reduction of CO2 involves a complex multi-electron transfer path, resulting in a large number of products such as carbon monoxide, methanol, methane, etc., how to construct a reasonable photocatalytic system to obtain high selectivity and high value-added fuels has become a great challenge in this field.

[0003] Photocatalytic reduction of CO2 refers to the process in which CO2 is reduced to form high-value-added chemicals and fuels under the action of a photocatalyst, through the conversion of a portion of photons into chemically active excited-state electrons, and then using chemical reactions. Therefore, the design of photocatalysts is crucial for improving the efficiency of photocatalytic reduction of CO2 and achieving efficient utilization of solar energy. Currently, most of the catalysts used are zero-dimensional powder structures, which are prone to agglomeration in liquid environments, making it difficult to separate them from the reaction system, resulting in poor recyclability and secondary pollution to the reaction system.

[0004] In order to solve the problem of agglomeration of zero-dimensional catalysts, researchers have begun to study two-dimensional catalysts, which can enhance light absorption and avoid agglomeration of active substances by constructing active sites on two-dimensional planar substrates, thereby improving the performance of various optoelectronic devices. However, the low specific surface area of planar substrates limits the assembly amount of active centers, making it difficult to maximize the light absorption capacity of the system. Later, researchers found that constructing nanostructures such as nanorod and nanoneedle arrays on the surface of planar substrates can provide a larger surface area to load more active substances; however, constructing very thin nano-scale structures on two-dimensional planar substrates in actual production requires high process requirements and is difficult to produce, has great limitations, and cannot obtain high-load active centers, and lacks the highly required macro-mass transfer channels in chemical reactions such as photocatalysis.

[0005] Therefore, it is very necessary to break through the two-dimensional plane substrate, design and build a layered structure to obtain a larger surface area and load more active substances. On the one hand, more hierarchical structures can significantly enhance the light absorption capacity of the system; on the other hand, the macroscopic and microscopic structures are systematically adjusted at the device level, which can provide sufficient surface active sites and effective mass transfer channels for sunlight-driven chemical reactions at the same time, which is also crucial for efficient use of solar energy. Therefore, it is necessary to provide a new technical solution to overcome the above defects. SUMMARY

[0006] The purpose of the present application is to provide a biomimetic vertical 3D printed photocatalyst and its preparation method and application which can effectively solve the above technical problems.

[0007] In order to achieve the purpose of the present application, the following technical solutions are adopted:

[0008] A biomimetic vertical 3D printed photocatalyst, which uses Al2O3 array as a carrier and three-dimensional skeleton, and is prepared by growing CdIn2S4 on the surface of the Al2O3 array.

[0009] A method for preparing the photocatalyst as described above, comprising the following steps:

[0010] Step 1: preparing an Al2O3 array;

[0011] Step 2: preparing a CdIn2S4 solution;

[0012] Step 3: placing the Al2O3 array and the CdIn2S4 solution into a hydrothermal reaction kettle for hydrothermal reaction, taking out the Al2O3 array after the reaction is completed, and washing and drying to obtain the photocatalyst.

[0013] Preferably, in step 1, the Al2O3 array is composed of the following raw materials by weight: main ceramic Al2O3 60-80 parts, auxiliary ceramic TiO2 5-10 parts, 3D printing carrier precursor driving resin 10-30 parts, and dispersant BYK-1100 0.1-5 parts.

[0014] Preferably, the 3D printing carrier precursor driving resin is composed of the following raw materials by weight: monomer PEGDA 35-40 parts, monomer HDDA 15-20 parts, monomer TMPTA 35-40 parts, and photoinitiator TPO 3-10 parts.

[0015] Preferably, the preparation method of the Al2O3 array is as follows:

[0016] S1: weigh monomer PEGDA, monomer HDDA and monomer TMPTA, pour into a glass beaker and stir until uniform, then add a photoinitiator TPO, ultrasonic treatment, and then put into a high-speed blender for stirring, thereby obtaining a 3D printing carrier precursor driving resin;

[0017] S2: weigh the 3D printing carrier precursor driving resin, main ceramic Al2O3, auxiliary ceramic TiO2 and dispersant, and put into a ball mill jar for ball milling, thereby obtaining a 3D printing ceramic slurry;

[0018] S3: pour the 3D printing ceramic slurry into a resin tank of a 3D printer, set the printer parameters, and perform 3D printing forming, after printing, wash the printed array with alcohol to remove the surface slurry, and dry to obtain a sintering precursor; put the sintering precursor into a muffle furnace for air calcination, thereby obtaining an Al2O3 array.

[0019] Preferably, in the step S3, the 3D printing data source model is an STL model, and the model is a cuboid on which an array composed of a plurality of circular cones is grown; the printer setting parameters are light intensity 3-5 mW / cm2, layer thickness 50 μm, exposure time 3-6 s, and printing form up-pull; and the sintering rate of the 3D printing carrier is 0.5-5 oC / min.

[0020] Preferably, in the step 2, the CdIn2S4 solution is prepared as follows: Cd(NO3)2.4H2O and In(NO3)3.4.5H2O are dissolved in deionized water, ultrasonic treatment is performed, then L-cysteine is added and magnetically stirred until completely dissolved, thereby obtaining a CdIn2S4 solution.

[0021] Preferably, the molar ratio of Cd(NO3)2.4H2O, In(NO3)3.4.5H2O and L-cysteine is 1:2:4.

[0022] Further, the application also provides a use of the photocatalyst as described above or the photocatalyst prepared by the method as described above for photocatalyzing CO2.

[0023] Compared with the prior art, the application has the following beneficial effects:

[0024] 1、The photocatalyst of the present application first introduces the concept of monolithic catalyst into the field of photocatalytic CO2 reduction, uses the Al2O3 array made by stereolithography 3D printing technology as the carrier and three-dimensional skeleton, grows CdIn2S4 on the array surface by hydrothermal method, thereby obtaining a biomimetic vertical type 3D printing photocatalyst with a three-dimensional structure, and the dense array increases the specific surface area of the catalyst, which can provide abundant surface reaction sites for light-driven chemical reactions, thereby effectively solving the defect that the specific surface area of the traditional catalyst is limited; meanwhile, the catalyst realizes high loading of active centers in the Z-axis direction and has a macro mass transfer channel, thereby effectively improving the catalytic activity.

[0025] 2、The photocatalyst of the present application has excellent CO2 photocatalytic reduction performance, and in the process of catalytic reduction of CO2 by using solar energy, the production amounts of CO and CH4 can reach 50.06 and 12.05 nmol·h -1 ·cm -2 .

[0026] 3、The photocatalyst of the present application has simple and easy-to-operate preparation process, and no difficult-to-handle solvent is introduced in the production process, the reaction condition is mild, green and environmentally friendly; meanwhile, when the photocatalyst of the present application is separated from the reaction system, no centrifugation process is needed, and it can be easily taken out from the reaction system, which is convenient and simple, easy to recycle, and will not cause secondary pollution to the reaction system. BRIEF DESCRIPTION OF DRAWINGS

[0027] In order to more clearly illustrate the technical solutions in the embodiments of the present application, the drawings needed in the embodiment description will be briefly introduced as follows.

[0028] Figure 1 A biomimetic vertical type 3D printing photocatalyst provided by the present application is in the form of three stages of model design, carrier preparation and hydrothermal loading; picture a is a three-dimensional data model of the 3D printing catalyst designed by 3D max; b is a picture of the 3D printing Al2O3 carrier after calcination; c is the catalyst 3D-CdIn2S4 / Al2O3 after hydrothermal treatment;

[0029] Figure 2 The photocatalytic CO2 reduction performance of different catalysts prepared in the embodiment part of the present application is shown in the figure;

[0030] Figure 3 The XRD spectrum of different catalysts prepared in the embodiment part of the present application is shown in the figure. DETAILED DESCRIPTION

[0031] In order to make the purpose, technical scheme and advantages of the embodiments of the present application more clear, the technical solutions in the embodiments of the present application will be described clearly and completely as follows, obviously, the described embodiments are part of the embodiments of the present application, but not all the embodiments.

[0032] The application provides a biomimetic vertical 3D printing photocatalyst, which takes an Al2O3 array as a carrier and a three-dimensional skeleton and is prepared by growing CdIn2S4 on the surface of the Al2O3 array.

[0033] Meanwhile, a method for preparing the photocatalyst is provided, and specifically comprises the following steps.

[0034] Step 1: preparing the Al2O3 array;

[0035] Step 2: preparing a CdIn2S4 solution;

[0036] Step 3: placing the Al2O3 array and the CdIn2S4 solution into a hydrothermal reaction kettle for hydrothermal reaction, taking out the Al2O3 array after the reaction, and cleaning and drying to obtain the photocatalyst.

[0037] In the step 1, the Al2O3 array is composed of the following raw materials in parts by weight: main body ceramic Al2O3 60-80 parts, auxiliary ceramic TiO2 5-10 parts, 3D printing carrier precursor driving resin 10-30 parts, and dispersant BYK-110 0.1-5 parts; the 3D printing carrier precursor driving resin is composed of the following raw materials in parts by weight: monomer PEGDA 35-40 parts, monomer HDDA 15-20 parts, monomer TMPTA 35-40 parts, and photoinitiator TPO 3-10 parts.

[0038] The preparation method of the Al2O3 array is as follows:

[0039] S1: weighing monomer PEGDA, monomer HDDA and monomer TMPTA, pouring them into a glass beaker and stirring uniformly, then adding photoinitiator TPO and performing ultrasonic treatment, and then placing them into a high-speed stirrer for stirring, to obtain the 3D printing carrier precursor driving resin;

[0040] S2: weighing the 3D printing carrier precursor driving resin, main body ceramic Al2O3, auxiliary ceramic TiO2 and dispersant, and placing them into a ball mill jar for ball milling, to obtain 3D printing ceramic slurry;

[0041] S3: pouring the 3D printing ceramic slurry into a resin tank of a 3D printer, setting the parameters of the printer, and performing 3D printing forming; after the printing is completed, the printed array is washed with alcohol to remove the slurry on the surface, and the sintering precursor is obtained after drying; the sintering precursor is placed into a muffle furnace for air calcination, to obtain the Al2O3 array.

[0042] In the step S3, the 3D printing data source model is an STL model, and the model is a cuboid on which an array composed of a plurality of circular cones is grown; the printer setting parameter is light intensity 3-5 mW / cm2, layer thickness 50 μm, exposure time 3-6 s, and printing form is up-pulling; and the sintering rate of the 3D printing carrier is 0.5-5 oC / min.

[0043] In the step 2, the CdIn2S4 solution is prepared as follows: Cd(NO3)2.4H2O and In(NO3)3.4.5H2O are dissolved in deionized water, ultrasonic treatment is performed, and then L-cysteine is added and magnetically stirred until completely dissolved, so as to obtain the CdIn2S4 solution; the molar ratio of Cd(NO3)2.4H2O, In(NO3)3.4.5H2O and L-cysteine is 1:2:4.

[0044] In addition, the application further provides a use of the photocatalyst or the photocatalyst prepared by the method for photocatalyzing CO2, and the photocatalyst can effectively improve the CO2 photocatalytic reduction performance in the process of photocatalyzing CO2, and high-yield high-value-added chemicals and fuels are obtained.

[0045] Example 1

[0046] 12 grams of monomer PEGDA, 6 grams of monomer HDDA and 12 grams of monomer TMPTA are weighed into a glass beaker and stirred uniformly to obtain a mixed resin; then 2g of photoinitiator TPO is placed in the mixed resin and ultrasonic treatment is performed for 5 min; then a high-speed dispersion machine is used for stirring, and the stirring rate is set to 500 rpm / min, and the stirring is continued for 30 min to obtain a 3D printing carrier precursor driving resin.

[0047] 19 grams of main ceramic Al2O3 powder (D50=1 μm) and 1 gram of auxiliary ceramic TiO2 (P25) are weighed as a base powder and uniformly mixed; 7.57 grams of 3D printing carrier precursor driving resin and 1 gram of dispersant BYK-110 are added and stirred into a uniform solution with a glass rod, and the solution is placed in a vertical planetary ball mill for ball milling for 8 h to obtain a photocuring 3D printing ceramic slurry.

[0048] The 3D printing ceramic slurry is poured into a resin tank of an LCD 3D printer, an ultraviolet LED light source with a wavelength of 405 nm is used as a light source, a 3D printing data source model is selected as an STL model, the model is a 20×20×1.5 mm cuboid on which an array composed of 100 circular cones with a bottom radius of 1 mm and a height of 3 mm is grown, 3D printer setting parameters are light intensity 5 mW / cm2, layer thickness 50 μm, exposure time 3-6 s, and printing form is up-pulling. 2, layer thickness 50 pm, exposure time 6 s, printing form is pull-up type; after printing is completed, the embryo is washed with alcohol to remove the slurry on the surface, and a sintering precursor is obtained after drying; the sintering precursor is placed in a muffle furnace for air calcination, the temperature is raised to 1200 DEG C at a rate of 1 DEG C / min and kept for 120 min, and then the temperature is lowered, to obtain a complete 3D printed carrier Al2O3 array.

[0049] Take 0.0616 g of Cd(NO3)2.4H2O and 0.1204 g of In(NO3)3.4.5H2O, dissolve them in 20 mL of deionized water, ultrasonic treatment for 5 min, then add 0.0968 g of L-cysteine and stir magnetically for 30 min until completely dissolved, to obtain a CdIn2S4 solution; the CdIn2S4 solution and the Al2O3 array are placed in a hydrothermal reaction kettle, heated to 180 DEG C and placed for 10 h, after the reaction is completed, the Al2O3 array is taken out, washed with deionized water and dried to obtain a photocatalyst.

[0050] Example 2

[0051] Take 10 g of monomer PEGDA, 7 g of monomer HDDA and 14 g of monomer TMPTA, pour them into a glass beaker and stir until uniform, to obtain a mixed resin, then put 1 g of photoinitiator TPO into the mixed resin, ultrasonic treatment for 5 min; then put it into a high-speed dispersing machine for stirring, the stirring rate is set to 500 rpm / min, and the stirring lasts for 30 min, to obtain a 3D printing carrier precursor driving resin.

[0052] Take 18 g of main ceramic Al2O3 powder (D50 = 1 pm) and 2 g of auxiliary ceramic TiO2 (P25) as the base powder, mix them uniformly; then add 6.57 g of 3D printing carrier precursor driving resin and 2 g of dispersant BYK-110, stir with a glass rod to form a uniform solution, and put it into a vertical planetary ball mill for ball milling for 8 h, to obtain a photocuring 3D printing ceramic slurry.

[0053] Pour the 3D printing ceramic slurry into the resin tank of an LCD 3D printer, use a UV LED light source with a wavelength of 405 nm, select a 3D printing data source model as an STL model, and the model is a 20x20x1.5 mm cuboid with 100 conical pyramids with a base radius of 1 mm and a height of 3 mm grown on the upper surface, to form an array; the 3D printer is set to a light intensity of 4 mW / cm 2 , layer thickness 50 pm, exposure time 6 s, printing form is pull-up type; after printing is completed, the embryo is washed with alcohol to remove the slurry on the surface, and a sintering precursor is obtained after drying; the sintering precursor is placed in a muffle furnace for air calcination, the temperature is raised to 1200 DEG C at a rate of 1 DEG C / min and kept for 120 min, and then the temperature is lowered, to obtain a complete 3D printed carrier Al2O3 array.

[0054] Take 0.0308 g of Cd(NO3)2.4H2O and 0.0602 g of In(NO3)3.4.5H2O dissolved in 20 mL of deionized water, after ultrasonic treatment for 5 min, 0.0484 g of L-cysteine is added and stirred magnetically for 30 min until completely dissolved, to obtain a CdIn2S4 solution, the CdIn2S4 solution and the Al2O3 array are placed in a hydrothermal reactor, heated to 180 degrees and placed for 10 h, the Al2O3 array is taken out, washed with deionized water, and dried to obtain a photocatalyst.

[0055] Example 3

[0056] Weigh 14 grams of monomer PEGDA, 6.5 grams of monomer HDDA and 10 grams of monomer TMPTA into a glass beaker and stir until uniform, then add 1.5 g of photoinitiator TPO to the mixed resin, ultrasonic treatment for 5 min, then put it into a high-speed disperser and stir at a speed of 500 rpm / min for 30 min, to obtain a 3D printing carrier precursor driving resin.

[0057] Weigh 18.5 grams of main ceramic Al2O3 powder (D50 = 1 μm) and 1.5 grams of auxiliary ceramic TiO2 (P25) as the matrix powder, mix well; add 7.57 grams of 3D printing carrier precursor driving resin and 1 gram of dispersant BYK-110, stir with a glass rod to form a uniform solution, and then put it into a vertical planetary ball mill for 8 h of ball milling, to obtain a photocurable 3D printing ceramic slurry.

[0058] Pour the 3D printing ceramic slurry into the resin tank of the LCD 3D printer, use a UV LED light source with a wavelength of 405 nm, select a 3D printing data source model of STL model, and the model is a cuboid with a length of 20 x 20 x 1.5 mm; the 3D printer is set at a light intensity of 4 mW / cm 2 , layer thickness 50 μm, exposure time 4 s, and printing form is pull-up type; after printing, rinse the embryo with alcohol to remove the slurry on the surface, dry to obtain a sintering precursor; place the sintering precursor in a muffle furnace for air calcination, with a heating rate of 1.5 ℃ / min to 1200 ℃ for 120 min, then cool down, to obtain a complete 3D printing carrier Al2O3 plate cuboid.

[0059] Take 0.0616 g of Cd(NO3)2.4H2O and 0.1204 g of In(NO3)3.4.5H2O dissolved in 20 mL of deionized water, after ultrasonic treatment for 5 min, 0.0968 g of L-cysteine is added and stirred magnetically for 30 min until completely dissolved, to obtain a CdIn2S4 solution; the CdIn2S4 solution and the Al2O3 array are placed in a hydrothermal reactor, heated to 180 degrees and placed for 10 h, the Al2O3 cuboid is taken out, washed with deionized water and dried to obtain a photocatalyst.

[0060] Comparative Example 1

[0061] Weigh 12 grams of monomer PEGDA, 6 grams of monomer HDDA and 12 grams of monomer TMPTA into a glass beaker and stir until uniform, to obtain a mixed resin, 2 g of photoinitiator TPO is placed in the mixed resin, ultrasonic treatment for 5 min, then placed in a high-speed disperser for stirring, the stirring rate is set to 500 rpm / min, and the stirring is continued for 30 min, to obtain a 3D printing carrier precursor driving resin.

[0062] Weigh 19 grams of main ceramic Al2O3 powder (D50 = 1 μm) and 1 gram of auxiliary ceramic TiO2 (P25) as the matrix powder, mix uniformly; add 7.57 grams of 3D printing carrier precursor driving resin and 1 gram of dispersant BYK-110, stir with a glass rod to form a uniform solution, and then place it in a vertical planetary ball mill for 8 h of ball milling, to obtain a photocurable 3D printing ceramic slurry.

[0063] Pour the 3D printing ceramic slurry into the resin tank of an LCD 3D printer, use a UV LED light source with a wavelength of 405 nm; select a 3D printing data source model as an STL model, the model is a 20x20x1.5 mm cuboid with 100 conical pyramids with a base radius of 1 mm and a height of 3 mm grown on it, forming an array; the 3D printer is set to a light intensity of 5 mW / cm 2 , a layer thickness of 50 μm, an exposure time of 6 s, and a printing form of pull-up type; after printing, rinse the embryo with alcohol to remove the slurry on the surface, and dry to obtain a sintering precursor; place the sintering precursor in a muffle furnace for air calcination, with a heating rate of 1 ℃ / min to 1200 ℃ for 120 min, then cool down, to obtain a 3D printed catalyst; the catalyst does not undergo a hydrothermal reaction.

[0064] Experimental Part

[0065] 1. The photocatalysts prepared by the above Examples 1-3 and Comparative Example 1 are used for photocatalytic CO2 reaction, and the yields of CH4 and CO are calculated, the results are shown in Figure 2 , by Figure 2It can be seen that the catalytic performance of the photocatalyst of Example 1 is better than that of the photocatalyst of Example 2, and the reason for studying it is that the CdIn2S4 added in Example 2 is less, thereby causing the active material load grown on the 3D printed carrier Al2O3 array to be less, resulting in lower activity.

[0066] The catalytic performance of the photocatalyst of Example 3 is also lower than that of the photocatalyst of Example 1, and the reason for studying it is that the photocatalyst of Example 3 is only a flat cuboid, without forming a three-dimensional catalyst form, and the load is less, resulting in a decrease in activity.

[0067] The catalytic performance of the photocatalyst of Comparative Example 1 is also lower than that of the photocatalyst of Example 1, and the reason for studying it is that the photocatalyst of Comparative Example 1 has no hydrothermal process, and no active center is grown on the surface, similar to a branch without leaves, and cannot form a complete biomimetic system, so the catalytic activity is poor.

[0068] 2, At the same time, the photocatalyst of Example 1 was detected, and the XRD spectrum as shown in Figure 3 was obtained, and the results showed that it not only had pure Al2O3 characteristic peaks, but also had characteristic peaks at 27.5° and 47.7°. Through standard card comparison, it was found that the characteristic peaks belonged to CdIn2S4. The above can show that the CdIn2S4 in the 3D-CdIn2S4 / Al2O3 catalyst is uniformly loaded on the Al2O3.

[0069] Various modifications to these examples will be apparent to those skilled in the art, and general principles defined herein can be applied to other embodiments without departing from the spirit or scope of the application.

Claims

1. A biomimetic vertical 3D printed photocatalyst, characterized by: The catalyst takes Al2O3 array as a carrier and three-dimensional skeleton, and is prepared by growing CdIn2S4 on the surface of the Al2O3 array; The preparation method comprises the following steps: Step 1: preparing the Al2O3 array; Step 2: preparing a CdIn2S4 solution; Step 3: placing the Al2O3 array and the CdIn2S4 solution into a hydrothermal reaction kettle for hydrothermal reaction, taking out the Al2O3 array after the reaction, and cleaning and drying to obtain the photocatalyst; The preparation method of the Al2O3 array is as follows: S1: weighing monomer PEGDA, monomer HDDA and monomer TMPTA, stirring them uniformly in a glass beaker, then adding a photoinitiator TPO for ultrasonic treatment, and then placing them in a high-speed stirrer for stirring, to obtain a 3D printing carrier precursor driving resin; S2: weighing the 3D printing carrier precursor driving resin, main ceramic Al2O3, auxiliary ceramic TiO2 and a dispersing agent, and placing them in a ball mill jar for ball milling, to obtain a 3D printing ceramic slurry; S3: pouring the 3D printing ceramic slurry into a resin tank of a 3D printer, setting the parameters of the printer, and performing 3D printing forming, then washing the formed array with alcohol to remove the slurry on the surface, and drying to obtain a sintering precursor; placing the sintering precursor in a muffle furnace for air calcination, to obtain the Al2O3 array; The preparation method of the CdIn2S4 solution is as follows: dissolving Cd(NO3)2.4H2O and In(NO3)3.4.5H2O in deionized water, performing ultrasonic treatment, then adding L-cysteine and stirring magnetically until completely dissolved, to obtain the CdIn2S4 solution.

2. The biomimetic vertical 3D printed photocatalyst according to claim 1, characterized in that: In step 1, the Al2O3 array is composed of the following raw materials by weight: main ceramic Al2O3 60-80 parts, auxiliary ceramic TiO2 5-10 parts, 3D printing carrier precursor driving resin 10-30 parts, and dispersing agent BYK-1100 0.1-5 parts.

3. The biomimetic vertical 3D printed photocatalyst according to claim 2, characterized in that: The 3D printing carrier precursor driving resin is composed of the following raw materials by weight: monomer PEGDA 35-40 parts, monomer HDDA 15-20 parts, monomer TMPTA 35-40 parts, and photoinitiator TPO 3-10 parts.

4. The biomimetic vertical 3D printed photocatalyst according to claim 1, characterized in that: In the step S3, the 3D printing data source model is an STL model, and the model is a cuboid on which an array composed of a plurality of circular cones is grown; the printer setting parameter is light intensity 3-5 mW / cm 2 , layer thickness 50 μm, exposure time 3-6 s, and printing form is up pull; and the sintering rate of the 3D printing carrier is 0.5-5 ℃ / min.

5. The biomimetic vertical 3D printed photocatalyst according to claim 1, wherein: The molar ratio of Cd(NO3)2.4H2O, In(NO3)3.4.5H2O and L-cysteine is 1:2:

4.

6. Use of the photocatalyst according to any one of claims 1-5 for photocatalyzing CO2.

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