3D printing structure and function integrated calcium oxide photocatalytic reactor and preparation method thereof
The integrated calcium oxide photocatalytic reactor with integrated functions was prepared through 3D printing technology, which solved the problem that calcium oxide could not be used as a catalyst for catalytic reactions, and achieved the efficient conversion of CO2 into high-value chemical products.
Patent Information
- Application Number
- CN202510314015.3
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-03-17
- Publication Date
- 2025-06-27
AI Technical Summary
Existing calcium oxide as a catalyst cannot undergo catalytic reactions and cannot effectively convert CO2 into high-value chemical products.
The integrated calcium oxide photocatalytic reactor with integrated functions was prepared by 3D printing technology, and the calcium carbonate powder and photocuring resin were mixed, and the dispersant, sintering aid and photoinitiator were added. After photocuring and sintering treatment, a calcium oxide photocatalytic reactor with oxygen defects was formed.
Functional modification of calcium oxide from an insulator to a semiconductor-like semiconductor with photocatalytic action can effectively adsorb and catalyze the conversion of CO2 into high-value chemical products such as CO and CH4. The yield of CO is 1.50-2.50 mmol g-1h-1, and the yield of CH4 is 0.15-0.30 mmol g-1h-1.
Smart Images
Figure CN120208646A_ABST
Abstract
Description
Technical Field
[0001] This application relates to the field of catalysts, and particularly to a 3D-printed integrated structure and function calcium oxide photocatalytic reactor and a preparation method thereof. Background Art
[0002] Photocatalytic technology can convert light energy and CO2 into valuable renewable energy through photocatalysts to solve energy shortages and the greenhouse effect. Traditional photocatalysts are expensive semiconductor materials such as titanium dioxide and zinc oxide, with high costs in large-scale industrial applications. Compared with semiconductor materials, calcium oxide, an insulator material with rich resources, has low costs and wide applications. And calcium oxide is a basic oxide, which is conducive to the adsorption and activation of CO2, thus promoting the catalytic reaction. However, since calcium oxide is an insulator and does not have catalytic functions, it cannot be used as a catalyst for catalytic reactions. Summary of the Invention
[0003] The main purpose of this application is to provide a 3D-printed integrated structure and function calcium oxide photocatalytic reactor and a preparation method thereof, aiming at the problem that existing calcium oxide cannot be used as a catalyst for catalytic reactions.
[0004] To achieve the above purpose, this application provides a preparation method of a 3D-printed integrated structure and function calcium oxide photocatalytic reactor, including: mixing calcium carbonate powder and photocurable resin to obtain a mixture; adding a dispersant, a sintering aid, and a photoinitiator to the mixture to obtain a calcium oxide precursor slurry; performing 3D printing on the calcium oxide precursor slurry to obtain a green sample; sequentially performing photocuring and sintering on the green sample to obtain a calcium oxide photocatalytic reactor with oxygen defects; wherein, the temperature in the sintering process is, after maintaining at 500 - 600 °C for 3 - 6 h, raising the temperature to 900 - 1300 °C and maintaining for 2 - 4 h.
[0005] Optionally, the mass fractions of each component in the calcium oxide precursor slurry are: 40% - 55% calcium carbonate powder, 45 - 55% photocurable resin, 1% - 4% dispersant, 2% - 6% sintering aid, 1% - 2% photoinitiator, and the sum of the above components is 100%.
[0006] Optionally, the preparation method of the green sample includes: performing 3D printing on the calcium oxide precursor slurry according to a preset structure model to obtain a green sample; wherein, the preset structure model includes at least one reaction cylinder.
[0007] Optionally, when the number of reaction cylinders is greater than 1, adjacent reaction cylinders are connected to each other and arranged in an array.
[0008] Optionally, the photocurable resin includes epoxy acrylate, polyurethane acrylate resin, polyester acrylate resin, or amino acrylate resin.
[0009] Optionally, the dispersant includes propylene glycol methyl ether acetate, polyvinylpyrrolidone, polyurethane-modified acrylate, ammonium polyacrylate or triethanolamine; the sintering aid includes silica, alumina or magnesia; the photoinitiator includes 2-hydroxy-2-methyl-1-phenylpropanone, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-2-(4-morpholinyl)-1-[4-(methylthio)phenyl]-1-propanone, 2-dimethylamino-2-benzyl-1-[4-(4-morpholinyl)phenyl]-1-butanone, 2-hydroxy-2-methyl-1-[4-(2-hydroxyethoxy)phenyl]-1-propanone, 2,4,6-trimethylbenzoyl-diphenylphosphine oxide, ethyl 2,4,6-trimethylbenzoyl phenylphosphinate or methyl benzoylformate.
[0010] Optionally, during the 3D printing process, the optical machine current is 5 - 12 mA, the bottom layer exposure time is 30 - 40 s, and the upper layer exposure time is 15 - 20 s.
[0011] Optionally, the photocuring is ultraviolet lamp curing, and the photocuring time is 60 - 120 min; the atmosphere during the sintering process is hydrogen.
[0012] To achieve the above object, the present application also provides a 3D printed structural and functional integrated calcium oxide photocatalytic reactor, which is characterized in that it is obtained by the above preparation method.
[0013] To achieve the above object, the present application also provides an application of the 3D printed structural and functional integrated calcium oxide photocatalytic reactor in the field of photocatalysis.
[0014] Compared with the prior art, the beneficial effects of the present application are as follows:
[0015] The preparation method of the 3D printed structural and functional integrated calcium oxide photocatalytic reactor of the present invention uses calcium carbonate as a precursor to prepare a 3D printed photocurable slurry. The obtained sample green body is cured by an ultraviolet lamp and sintered in a special atmosphere to form a calcium oxide light-concentrating structure with oxygen defects; the oxygen defects in calcium oxide will affect the band gap of calcium oxide, thereby realizing the functional modification of calcium oxide from an insulator to a semiconductor-like material with photocatalytic properties; the modified calcium oxide not only has a good adsorption effect on CO2, but can also be used as a catalyst to convert CO2 into chemical products with high utilization value such as CO and CH4, and the yield of CO is 1.50 - 2.50 mmol g -1 h -1 , and the yield of CH4 is 0.15 - 0.30 mmol g -1 h -1 .
[0016] The 3D printed integrated structural and functional calcium oxide photocatalytic reactor of the present invention belongs to a parabolic concentrating structure with an array feature; the concave parabolic structure can optimize the photon transmission inside the structure. When light shines on the concentrating structure from the top, the curved inner wall can enhance the reflection and absorption of light, making the light absorption rate reach 85%; at the same time, the array feature can expand the light absorption advantage of the structure and further improve the light utilization rate. Description of the Drawings
[0017] Figure 1 It is a process state change diagram of the preparation method of a 3D printed integrated structural and functional calcium oxide photocatalytic reactor of the present application; Figure 2 It is a model diagram of a single reaction cylinder in the reactor of the preparation method of a 3D printed integrated structural and functional calcium oxide photocatalytic reactor of the present application; Figure 3 It is a simulated light absorption diagram of the outer edge of a single reaction cylinder in the reactor of the preparation method of a 3D printed integrated structural and functional calcium oxide photocatalytic reactor of the present application; Figure 4 It is a simulated light absorption diagram of one inner wall of a single reaction cylinder in the reactor of the preparation method of a 3D printed integrated structural and functional calcium oxide photocatalytic reactor of the present application; Figure 5 It is a simulated light absorption diagram of the other inner wall of a single reaction cylinder in the reactor of the preparation method of a 3D printed integrated structural and functional calcium oxide photocatalytic reactor of the present application; Figure 6 It is an XRD diagram of the product obtained by the preparation method of a 3D printed integrated structural and functional calcium oxide photocatalytic reactor of the present application; Figure 7 It is a test diagram of the reactor obtained by the preparation method of a 3D printed integrated structural and functional calcium oxide photocatalytic reactor of the present application.
[0024] The realization, functional characteristics and advantages of the purpose of the present application will be further described with reference to the embodiments and the accompanying drawings. Detailed Embodiments
[0025] To make the purpose, technical solutions and advantages of the present application clearer, the technical solutions in the present application will be clearly and completely described below with reference to the accompanying drawings in the present application. Obviously, the described embodiments are part of the embodiments of the present application, rather than all of the embodiments. Based on the embodiments in the present application, all other embodiments obtained by those of ordinary skill in the art without making creative efforts belong to the scope of protection of the present application.
[0026] The first embodiment of the present invention provides a preparation method of a 3D printing integrated structural and functional calcium oxide photocatalytic reactor, which specifically includes the following steps:
[0027] Step S1: Mix calcium carbonate powder and photocurable resin to obtain a mixture; add a dispersant, a sintering aid, and a photoinitiator to the mixture to obtain a calcium oxide precursor slurry; wherein, the mixing time of the calcium carbonate powder and the photocurable resin is 8-10h, and the mixing time of the mixture with the dispersant, the sintering aid, and the photoinitiator is 2-3h.
[0028] Further, the mass fractions of the components in the calcium oxide precursor slurry are: 40%-55% calcium carbonate powder, 45-55% photocurable resin, 1%-4% dispersant, 2%-6% sintering aid, 1%-2% photoinitiator, and the sum of the above components is 100%.
[0029] Exemplarily, the photocurable resin includes epoxy acrylate, polyurethane acrylate, polyester acrylate, or amino acrylate. The dispersant includes propylene glycol methyl ether acetate, polyvinylpyrrolidone, polyurethane-modified acrylate, ammonium polyacrylate, or triethanolamine. The sintering aid includes silica, alumina, or magnesia. The photoinitiator includes 2-hydroxy-2-methyl-1-phenylpropanone, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-2-(4-morpholinyl)-1-[4-(methylthio)phenyl]-1-propanone, 2-dimethylamino-2-benzyl-1-[4-(4-morpholinyl)phenyl]-1-butanone, 2-hydroxy-2-methyl-1-[4-(2-hydroxyethoxy)phenyl]-1-propanone, 2,4,6-trimethylbenzoyl-diphenylphosphine oxide, 2,4,6-trimethylbenzoyl phenylphosphonic acid ethyl ester, or methyl benzoylformate.
[0030] Step S2: Perform 3D printing on the calcium oxide precursor slurry to obtain a sample green body;
[0031] Specifically, during the 3D printing process, the light machine current is 5-12mA, the bottom layer exposure time is 30-40s, and the upper layer exposure time is 15-20s. The sample green body is obtained by performing 3D printing on the calcium oxide precursor slurry according to a preset structural model; wherein, the preset structural model includes at least 1 reaction cylinder. Further, when the number of reaction cylinders is greater than 1, the outer side walls of adjacent reaction cylinders are connected to each other and arranged in an array. Exemplarily, the cross-sectional shape of the reaction cylinder can be circular.
[0032] In this embodiment, the preset structural model is formed by connecting multiple reaction cylinders arranged in an array, forming a parabolic concentrating structure with an array feature. The concave parabolic structure (i.e., the side wall of the reaction cylinder) can optimize the photon transmission inside the structure; when light shines on the concentrating structure from above, the curved inner wall can enhance the reflection and absorption of light, making the light absorption rate reach 85%. At the same time, the array feature can expand the light absorption advantage of the structure and further improve the light utilization rate.
[0033] Step S3: The sample green body is successively subjected to photocuring and sintering to obtain a calcium oxide photocatalytic reactor with oxygen defects; among them, the temperature during the sintering process is, after holding at 500 - 600 °C for 3 - 6 h, heating up to 900 - 1300 °C and holding for 2 - 4 h. The sintering atmosphere includes hydrogen. Further, the sintering atmosphere also includes argon or nitrogen, that is, a mixed gas of argon and hydrogen, or nitrogen and hydrogen.
[0034] Specifically, the photocuring is ultraviolet lamp curing, the photocuring time is 60 - 120 min, and the curing temperature is room temperature, that is, 20 - 30 °C.
[0035] In this embodiment, calcium carbonate is used as a precursor to prepare a 3D printing photocurable slurry to obtain a printed green body, which is then subjected to ultraviolet lamp curing and sintering in a special atmosphere to form a calcium oxide concentrating structure. During the sintering process, the calcium carbonate in the sample green body is heated to produce carbon dioxide and calcium oxide. At the same time, sintering in a mixed atmosphere containing hydrogen, the amorphous carbon and hydrogen formed by the decomposition of the resin in the printed green body react with the oxygen atoms in calcium oxide as reducing agents at the same time, causing the oxygen atoms on the surface of calcium oxide to escape, forming oxygen defects, and these oxygen defects will affect the band gap of calcium oxide, thereby realizing the functional modification of calcium oxide from an insulator to a semiconductor with photocatalytic properties. The modified calcium oxide not only has a good adsorption effect on CO2, but can also be used as a catalyst to convert CO2 into CO and CH4.
[0036] Example 1 prepares a catalytic reactor containing oxygen defects, and the change state during the reaction process is shown in Figure 1 , specifically as follows;
[0037] Mix 40% by mass of calcium carbonate powder and 55% of polyester acrylate resin and stir for 8 h until the calcium carbonate powder and the resin are evenly mixed to obtain a mixture; add 2% of triethanolamine, 2% of silicon dioxide, and 1% of methyl benzoylformate to the mixture and stir for 2 h to prepare a precursor slurry suitable for photocurable 3D printing, as shown in Figure 1 (a);
[0038] According to Figure 13D printing was carried out on the preset structural model shown in (b), with dimensions of 25 mm × 25 mm × 3 mm. The preset structural model is an array structure composed of 9×9 light - collecting structural units; the data of this preset structural model was imported into a CeraForm 100 ceramic 3D printer. The light machine current was set to 8 mA, the bottom - layer exposure time was 40 s, and the upper - layer exposure time was 20 s. The three - dimensional printing program was started, and the precursor slurry was deposited on the loading platform in a layer - by - layer stacking manner. After printing, the obtained sample was dried to obtain a sample green body, as shown in Figure 1 (c), with structural dimensions of 25 mm × 25 mm × 3 mm. The obtained sample green body was cured under an ultraviolet lamp for 120 min, and then placed in a tube furnace. Under a mixed atmosphere of argon and hydrogen, it was first heated from room temperature to 600 °C at a rate of 3 °C / min and held for 4 h, and then heated to 1350 °C and held for 3 h. After sintering, it was naturally cooled to room temperature to obtain a catalytic reactor containing oxygen defects, as shown in Figure 1 (d), with the size shrunk to 15 mm × 15 mm × 2.5 mm. From Figure 1 (c) and Figure 1 (d) comparison, it can be seen that Figure 1 the pure calcium oxide without sintering in (c) is white. Since the calcium oxide after sintering contains oxygen defects, therefore Figure 1 the reactor in (d) presents a light yellow color.
[0039] Light absorption simulation was carried out on a single parabolic light - collecting structure (i.e., a single reaction cylinder body) in the reactor obtained in this embodiment. Figure 2 It is a model diagram of a single parabolic light - collecting structure. Figure 3 It is a light absorption simulation diagram of the outer - ring surface (the outer edge of a single reaction cylinder). It can be seen from Figure 3 that for the horizontal outer - ring surface, the light absorption rate is only 80%. Figures 4 - 5 They are respectively light absorption simulation diagrams of the two inner - side wall surfaces. It can be seen from the figures that through the inner - surface structure design of the parabola, the photon transmission is optimized, the curved surface enhances the reflection of light, and the light absorption rate can reach 85%, improving the utilization rate of light.
[0040] Component analysis was carried out on the sample green body and the reactor obtained in this embodiment, and the results are shown in Figure 6 . It can be seen from Figure 6 a that the main component of the sample green body before sintering is calcium carbonate. Figure 6 It can be seen from b that the main component after sintering is calcium oxide, indicating that calcium carbonate gradually decomposes to form calcium oxide during the sintering process.
[0041] Traditional calcium oxide powder and the reactor obtained in this embodiment were tested, and the results are as shown in Figure 7 shown in Figure 7(a) is the test result of the oxygen defect characteristics of the reactor obtained in this embodiment. It can be seen from the figure that there is an obvious signal peak at g = 2.003, and this signal peak is the characteristic peak of oxygen defects, indicating that oxygen defects have occurred in the calcium oxide sample.
[0042] Example 2
[0043] Mix 42% calcium carbonate powder and 48% epoxy acrylate by stirring for 10 h until the calcium carbonate powder and the resin are evenly mixed to obtain a mixture; add 3% ammonium polyacrylate, 5% magnesium oxide, and 2% 2,4,6-trimethylbenzoyl-diphenylphosphine oxide to the mixture and stir for 2 h to prepare a precursor slurry suitable for photocuring 3D printing.
[0044] Import the preset structural model data into a 3D printer, which is a CeraForm 100 ceramic 3D printer. Set the optical machine current to 10 mA, the bottom layer exposure time to 34 s, and the upper layer exposure time to 17 s. Start the three-dimensional printing program. The precursor slurry is deposited on the loading platform in a layer-by-layer stacking manner. After printing, dry the obtained specimen to obtain a specimen green body. Cure the obtained specimen green body under ultraviolet light for 120 min, then place it in a tube furnace. Under a mixed atmosphere of argon and hydrogen, first heat from room temperature to 500 °C at a rate of 4 °C / min and hold for 6 h, then raise the temperature to 1300 °C and hold for 4 h. After sintering, cool naturally to room temperature to obtain a catalytic reactor containing oxygen defects.
[0045] Example 3
[0046] Mix 50% calcium carbonate powder and 45% polyurethane acrylate resin by stirring for 8 h until the calcium carbonate powder and the resin are evenly mixed to obtain a mixture; add 2% polyvinylpyrrolidone, 2% alumina, and 1% 2-hydroxy-2-methyl-1-phenylpropanone to the mixture and stir for 2 h to prepare a precursor slurry suitable for photocuring 3D printing.
[0047] Import the preset structural model data into a 3D printer, which is a CeraForm 100 ceramic 3D printer. Set the optical machine current to 12 mA, the bottom layer exposure time to 30 s, and the upper layer exposure time to 15 s. Start the three-dimensional printing program. The precursor slurry is deposited on the loading platform in a layer-by-layer stacking manner. After printing, dry the obtained specimen to obtain a specimen green body. Cure the obtained specimen green body under ultraviolet light for 60 min, then place it in a tube furnace. Under a mixed atmosphere of argon and hydrogen, first heat from room temperature to 550 °C at a rate of 5 °C / min and hold for 5 h, then raise the temperature to 1250 °C and hold for 3 h. After sintering, cool naturally to room temperature to obtain a catalytic reactor containing oxygen defects.
[0048] The second embodiment of the present invention provides a 3D printed integrated structural and functional calcium oxide photocatalytic reactor, which is obtained by the preparation method described above.
[0049] The third embodiment of the present invention provides an application of a 3D printed integrated structural and functional calcium oxide photocatalytic reactor in the field of photocatalysis.
[0050] Specifically, the reactor obtained by the above embodiment can be used for the catalytic reduction of CO2. In the catalytic reduction reaction of CO2, the yield of CO is 1.50 - 2.50 mmol g -1 h -1 , and the yield of CH4 is 0.15 - 0.30 mmol g -1 h -1 .
[0051] The specific method is as follows: First, place the calcium oxide photocatalytic reactor in a sealed quartz glass reaction chamber, and inject a certain amount of water vapor into the reaction chamber. Subsequently, use high-purity CO2 (purity up to 99.999%) and a vacuum pump to perform the charging and discharging operation on the reaction chamber, repeating 3 times. Inject a certain amount of high-purity CO2 into the reaction chamber and maintain the pressure at 0.1 MPa. With the help of a 300W Xe arc lamp, irradiate the sample through the quartz window for a specific duration to simulate sunlight. After the reaction lasts for a certain time, extract 2 ml of gas from the reaction chamber for measuring the product yield. The products are detected by gas chromatography (7890B, Agilent). Among them, gaseous products such as CH4, C2H4, CO, and CO2 are detected using a flame ionization detector (FID). The photocatalytic CO2 reduction performance diagram is as Figure 7 (b). As can be seen from the figure, the yield of CO is 1.56 mmol g -1 h -1 , and the yield of CH4 is 0.17 mmol g -1 h -1 . The traditional calcium oxide powder does not produce CO and CH4, thus proving that calcium oxide is an insulator and does not have photocatalytic activity.
[0052] The above are only the preferred embodiments of the present application, and do not limit the patent scope of the present application. Any equivalent structural or equivalent process transformation made using the content of the specification and drawings of the present application, or directly or indirectly applied in other related technical fields, shall be equally included in the patent protection scope of the present application.
Claims
1. A method for preparing a 3D printed structure-function integrated calcium oxide photocatalytic reactor, characterized in that: include: Mixing calcium carbonate powder and light-curable resin to obtain a mixture; adding a dispersant, a sintering aid, and a photoinitiator to the mixture to obtain a calcium oxide precursor slurry; Performing 3D printing on the calcium oxide precursor slurry to obtain a sample blank; The sample green body is sequentially subjected to photocuring and sintering to obtain a calcium oxide photocatalytic reactor having oxygen defects; The temperature of the sintering process is, after being kept at 500-600°C for 3-6 hours, the temperature is increased to 900-1300°C and kept at this temperature for 2-4 hours.
2. The method for preparing the 3D printed structure-function integrated calcium oxide photocatalytic reactor according to claim 1, characterized in that: The mass fractions of the components in the calcium oxide precursor slurry are: 40%-55% calcium carbonate powder, 45-55% photocurable resin, 1%-4% dispersant, 2%-6% sintering aid, 1%-2% photoinitiator, and the sum of the above components is 100%.
3. The method for preparing the 3D printed structure-function integrated calcium oxide photocatalytic reactor according to claim 1, characterized in that: The method for preparing the sample blank comprises: According to the preset structural model, the calcium oxide precursor slurry is 3D printed to obtain a sample blank; Wherein, the preset structural model includes at least one reaction cylinder.
4. The method for preparing the 3D printed structure-function integrated calcium oxide photocatalytic reactor according to claim 1, characterized in that: When the number of the reaction cylinders is greater than 1, adjacent reaction cylinders are connected to each other and arranged in an array.
5. The method for preparing the 3D printed structure-function integrated calcium oxide photocatalytic reactor according to claim 1, characterized in that: The photocurable resin includes epoxy acrylate, polyurethane acrylate, polyester acrylate or amino acrylate.
6. The method for preparing the 3D printed structure-function integrated calcium oxide photocatalytic reactor according to claim 1, characterized in that: The dispersant includes propylene glycol methyl ether acetate, polyvinyl pyrrolidone, polyurethane modified acrylate, ammonium polyacrylate or triethanolamine; The sintering aid includes silicon dioxide, aluminum oxide or magnesium oxide; The photoinitiator includes 2-hydroxy-2-methyl-1-phenylpropanone, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-2-(4-morpholinyl)-1-[4-(methylthio)phenyl]-1-propanone, 2-dimethylamino-2-benzyl-1-[4-(4-morpholinyl)phenyl]-1-butanone, 2-hydroxy-2-methyl-1-[4-(2-hydroxyethoxy)phenyl]-1-propanone, 2,4,6-trimethylbenzoyl-diphenylphosphine oxide, ethyl 2,4,6-trimethylbenzoylphenylphosphonate or methyl benzoylformate.
7. The method for preparing the 3D printed structure-function integrated calcium oxide photocatalytic reactor according to claim 1, characterized in that: During the 3D printing process, the photomechanical current is 5-12 mA, the bottom layer exposure time is 30-40 s, and the top layer exposure time is 15-20 s.
8. The method for preparing the 3D printed structure-function integrated calcium oxide photocatalytic reactor according to claim 1, characterized in that: The light curing is ultraviolet light curing, and the light curing time is 60-120 minutes; The atmosphere during the sintering process is hydrogen.
9. A 3D printed structure and function integrated calcium oxide photocatalytic reactor, characterized in that: The method is obtained by the preparation method according to any one of claims 1 to 8.
10. Application of the 3D printed structure-function integrated calcium oxide photocatalytic reactor according to claim 8 in the field of photocatalysis.