A catalyst based on BP25@ZEO-1 and a preparation method and application thereof
By preparing the BP25@ZEO-1 catalyst, the problems of easy aggregation and encapsulation of traditional titanium dioxide photocatalytic materials were solved, and a highly efficient and stable CO2 reduction CO process was achieved, improving the activity and selectivity of the catalyst.
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- JILIN UNIVERSITY
- Filing Date
- 2025-11-15
- Publication Date
- 2026-06-05
AI Technical Summary
Traditional semiconductor titanium dioxide photocatalytic materials are limited in their widespread application due to the easy aggregation of nanoparticles and short separation time, and the difficulties in the synthesis method of encapsulating them in zeolite have not been effectively solved.
P25 was loaded onto ZEO-1 using a urea co-precipitation method. The catalyst was prepared by hydrothermal synthesis and modification with sodium borohydride. Black titanium dioxide was encapsulated with ultraporous zeolite to form a tightly bound composite structure, which prevented agglomeration and optimized the reaction microenvironment.
It achieves high specific surface area and active site exposure, improves CO2 gas enrichment and photocatalytic activity, enhances catalyst stability and selectivity, and improves CO2 reduction CO product yield and titanium dioxide utilization.
Smart Images
Figure CN122141733A_ABST
Abstract
Description
Technical Field
[0001] This invention relates to the technical field of photocatalysis in the preparation of ultraporous zeolites, and more specifically, to a catalyst based on BP25@ZEO-1, its preparation method, and its application. Background Technology
[0002] Environmental pollution and energy crisis are major problems facing the world today. As an environmentally friendly material, photocatalytic materials have shown broad application prospects in environmental governance and energy conversion due to their green and efficient characteristics.
[0003] However, the widespread application of traditional semiconductor titanium dioxide (P25) photocatalytic materials is limited by drawbacks such as easy agglomeration of nanoparticles and short separation time. Loading semiconductors onto different support materials can effectively solve the problems of agglomeration and low efficiency. Among various support materials, insulating porous supports have become a research hotspot due to their ability to expose more active centers and improve light scattering.
[0004] Zeolites are crystalline porous materials with important industrial applications. Among them, macroporous zeolites (with more than 12-membered rings) can maintain high specific surface area and adsorption capacity, abundant acidic sites, photochemical stability and other advantages.
[0005] Furthermore, the spatial confinement of the zeolite framework allows for size and quantum confinement effects on guest molecules, stabilizing the external environment of photocatalytically active materials and enhancing catalytic activity. The abundant and regular micropores and cage-like structure of zeolite molecular sieves allow most visible and ultraviolet light to pass through, facilitating the utilization of light energy by the photocatalyst. Their high specific surface area effectively disperses photocatalytically active materials, preventing waste, inhibiting catalyst aggregation, and reducing the recombination rate of the photogenerated support. Zeolite molecular sieves also help reactants accumulate at the photocatalytically active centers, increasing the reaction rate and facilitating catalyst recovery.
[0006] However, due to the excessively large size of P25 nanoparticles, which far exceeds the open pore windows of molecular sieves, the synthesis method of encapsulating them in zeolite has always been a technical challenge. Summary of the Invention
[0007] The purpose of this invention is to overcome the shortcomings of the prior art and provide a reasonable encapsulation method that successfully introduces large-diameter titanium dioxide nanoparticles, while modifying the encapsulated material to further adjust the selectivity of the product.
[0008] The above-mentioned technical objective of the present invention is achieved through the following technical solution:
[0009] The present invention provides a catalyst based on BP25@ZEO-1, wherein the catalyst based on BP25@ZEO-1 is a catalyst of black titanium dioxide encapsulated in ultraporous zeolite.
[0010] The mass fraction of titanium dioxide is 2% to 14%.
[0011] This invention also provides a method for preparing a catalyst based on BP25@ZEO-1, comprising the following steps:
[0012] Synthetic seed crystals: P25 was loaded onto ZEO-1 using the urea co-precipitation method to obtain P25 / ZEO-1 composite seed crystals;
[0013] The template agent was evenly dispersed in water, and silicon source, aluminum source, halide, P25 / ZEO-1 composite seed crystal and the remaining water were added. The mixture was stirred evenly to obtain a gel-like mixture.
[0014] The gel-like mixture was loaded into a hydrothermal synthesis reactor and reacted at 180~200℃ for 3~21 days. After washing and drying, P25@ZEO-1 material was obtained.
[0015] The BP25@ZEO-1 catalyst was obtained by mixing P25@ZEO-1 material with sodium borohydride, grinding and calcining.
[0016] Furthermore, the template agent is tricyclohexylmethylphosphine, prepared by the following method:
[0017] Tricyclohexylphosphine was reacted with iodomethane at room temperature for 2-5 days, followed by rotary evaporation and drying to obtain the template agent.
[0018] Furthermore, in the P25 / ZEO-1 composite seed crystal, the molar ratio of P25 to ZEO-1 is 1:(3~7).
[0019] Furthermore, the ZEO-1 is a ZEO-1-Na type zeolite with a silica-alumina ratio of 25~50.
[0020] Furthermore, in the gel mixture, the molar ratio of silicon source: template agent: aluminum source: sodium chloride: P25 / ZEO-1 composite seed crystal is 1:0.5:0.04:0.01:0.01.
[0021] Furthermore, the P25 is a nanoscale mixed crystal titanium dioxide composed of anatase and rutile in a ratio of approximately 80:20, with a particle size of 10~20nm.
[0022] The present invention also provides an application of a BP25@ZEO-1-based catalyst, wherein the BP25@ZEO-1-based catalyst is used for photocatalytic reduction of CO from CO2.
[0023] Furthermore, the application of BP25@ZEO-1-based catalysts includes the following steps:
[0024] The BP25@ZEO-1-based catalyst was dissolved in ethanol, sonicated, and then dropped onto a quartz plate, air-dried, and placed into a photocatalytic reactor.
[0025] Add water dropwise into the photocatalytic reactor;
[0026] A gas containing CO2 is introduced into the photocatalytic reactor and then sealed.
[0027] Place the device under a xenon lamp for illumination;
[0028] The condensation process continues throughout.
[0029] Furthermore, based on the application of the BP25@ZEO-1 catalyst, the CO2-containing gas can be pure CO2 or a mixture of CO2 and N2 in different proportions.
[0030] In summary, the present invention has the following beneficial effects:
[0031] (1) The BP@ZEO-1 catalyst synthesized in this invention is an ultraporous zeolite molecular sieve with a high specific surface area and adsorption capacity, which can expose more active sites and enrich CO2 gas. Due to its good photocatalytic activity, the encapsulated titanium dioxide reduces the CO2 gas enriched inside the molecular sieve to CO, resulting in a high product yield and high titanium dioxide utilization. It also has high activity and high stability.
[0032] (2) The BP@ZEO-1 catalyst synthesized in this invention has a wider range of applicability under various photocatalytic conditions due to the more hydrophilic nature of the molecular sieve. The content of titanium dioxide is controllable, and the mass fraction is adjustable within the range of 2-14%. The silicon-to-aluminum ratio is adjustable, and the influence of the molecular sieve microenvironment on the photocatalytic CO2 reduction is also controlled.
[0033] (3) The BP@ZEO-1 catalyst synthesized in this invention contains cations used by the molecular sieve to balance the framework charge, which can act as an electron compensator to transfer electrons to the titanium dioxide end, thereby improving the reaction performance at the reduction end. In addition, it also helps to separate photogenerated electrons and holes, reduces the recombination probability, improves photocatalytic efficiency, and can more fully utilize solar energy to drive the CO2 reduction reaction. Attached Figure Description Figure 1 This is a flowchart illustrating the preparation process for an example. Figure 2 The XRD pattern of the catalyst based on BP25@ZEO-1 is shown. Figure 3The image shows the NMR spectrum of the BP25@ZEO-1-based catalyst. Figure 4 The N2 adsorption diagram is shown for the catalyst based on BP25@ZEO-1. Detailed Implementation
[0034] To further illustrate the technical means and effects adopted by the present invention to achieve the intended purpose, the specific implementation methods, features and effects of a catalyst based on BP25@ZEO-1, its preparation method and application, proposed according to the present invention are described in detail below.
[0035] This invention employs a seed-assisted method with 2-14% P25 loading, uniformly dispersing the seed crystals in an alkaline gel system to allow them to nucleate around the seed crystals. A hydrothermal synthesis method is used to achieve uniform growth of silica around titanium dioxide, ensuring that the titanium dioxide particle size and distribution in the BP25@ZEO-1 catalyst are relatively uniform.
[0036] In existing technologies, titanium dioxide (TiO2) is generally limited to the role of a reaction inert support or secondary auxiliary structure, and its core function is to support active substances rather than directly participate in catalytic reactions.
[0037] When used as an inert support, existing technologies typically fabricate TiO2 (such as ordinary P25) into porous structures or nanoparticles, which are only used to support metal ions (such as Au, Cu, Ni, etc.), metal oxides (such as Co3O4, ZnO, etc.) or other semiconductors (such as g-C3N4). TiO2 itself does not have or only has very weak catalytic activity, and the real catalytic reaction depends on the active components supported on its surface.
[0038] Even in the few technologies that allow TiO2 to participate in the reaction, it is mostly used as an auxiliary light absorber to optimize charge separation by forming a heterojunction with the load, rather than as a core active center.
[0039] In this invention, the ultra-large porous ZEO-1 molecular sieve serves as the support, and black titanium dioxide (BP25) is the core active component. The function of ZEO-1 is not to support the active material, but rather to optimize the reaction microenvironment for BP25 through its ultra-large pore structure, high specific surface area, and surface acidic sites. This includes enhancing CO2 adsorption to increase local reactant concentration, suppressing byproduct formation through pore sieving effect, and preventing BP25 nanoparticle aggregation to maintain active site exposure. BP25, on the other hand, is the core unit directly responsible for the photocatalytic CO2 reduction reaction. Its visible light absorption capacity and long carrier lifetime, after modification with sodium borohydride, are the key driving force for the reaction, eliminating the reliance on other supports to activate catalytic activity.
[0040] In existing technologies, the active components of TiO2-related catalytic systems have significant limitations in their form and mode of action, making it impossible to simultaneously achieve activity, stability, and selectivity.
[0041] If TiO2 is used as an inert support, the loaded metal ions / metal oxides are mostly in the form of surface adhesion. These active components are prone to agglomeration, shedding or redox deactivation during the reaction process, resulting in poor catalyst cycle stability. At the same time, the active components are only distributed on the TiO2 surface, and the contact with the reactants depends on surface diffusion. The reaction efficiency is limited by the loading amount and dispersion uniformity.
[0042] If metal ions are loaded onto the surface of TiO2 to form a heterojunction, the core objective of the existing technology is to optimize charge separation (such as TiO2 forming a heterojunction with g-C3N4 to promote the transfer of photogenerated electrons to g-C3N4). However, the light absorption range of TiO2 itself is still limited to ultraviolet light, and the heterojunction interface is prone to performance degradation due to the rebound of charge recombination rate. Furthermore, it cannot solve the problems of weak CO2 adsorption and many by-products.
[0043] This invention achieves a breakthrough in the form of active components by hydrothermally growing ultra-large pores of ZEO-1 encapsulating BP25.
[0044] BP25 is not attached to the surface of ZEO-1, but is encapsulated and wrapped by the channels or framework of ZEO-1. This form can fundamentally avoid the aggregation and shedding of BP25. At the same time, the channels of ZEO-1 provide a three-dimensional reaction space for BP25. The reactant CO2 can be rapidly diffused to the surface of BP25 through the channels, greatly improving the utilization rate of active sites.
[0045] More importantly, BP25 itself is a modified and activated active unit (not ordinary TiO2), and its black titanium structure already has visible light response and low charge recombination rate, so it does not need to rely on other supports. The addition of ZEO-1 is not to assist charge separation, but to directly optimize the entire process of reactant adsorption-product desorption, forming a synergistic mechanism in which the active component (BP25) is responsible for catalytic reaction and the support (ZEO-1) is responsible for microenvironment regulation. This is completely different from the existing technology that relies solely on the active component or heterojunction.
[0046] In existing technologies, the structural design goals of TiO2-based catalytic materials are mostly focused on improving single properties (such as charge separation efficiency and active component dispersion), lacking consideration for the synergistic effect of multiple properties.
[0047] For example, to increase the metal ion loading, existing technologies may increase the specific surface area of TiO2, but the excessively porous structure will lead to non-selective CO2 adsorption (adsorbing moisture and impurities at the same time); to broaden light absorption, multiple semiconductors may be introduced to form a heterojunction, but the complex interface structure will increase the preparation difficulty and make it difficult to control the product selectivity.
[0048] Ultimately, existing catalytic systems often face the problem of sacrificing some aspects for others. For example, while improving light absorption, they reduce stability; while increasing activity, they cannot suppress the generation of byproducts (such as H2 and CH4), making it difficult to meet the comprehensive requirements of high efficiency, high selectivity, and high stability in photocatalytic CO2 reduction.
[0049] This invention addresses several pain points of existing technologies by encapsulating BP25 in an integrated structure with ultra-large pores of ZEO-1: For weak light absorption: BP25's black titanium structure directly covers the visible light region, eliminating the need for additional semiconductor modification; For rapid charge recombination: BP25's inherent defect structure inhibits recombination, while the porous environment of ZEO-1 further reduces charge loss; For insufficient CO2 adsorption: ZEO-1's high specific surface area and porous adsorption sites enhance CO2 capture, increasing local reactant concentration; For low product selectivity: ZEO-1's pore sieving effect (matching CO molecule diameter) and surface acidic sites (guiding reaction pathways) precisely suppress byproduct formation; For poor stability: ZEO-1's encapsulation structure protects BP25 from aggregation and leakage, extending cycle life.
[0050] Therefore, this specific embodiment first provides a catalyst based on BP25@ZEO-1 provided by the present invention, wherein the catalyst based on BP25@ZEO-1 is a catalyst of black titanium dioxide encapsulated in ultra-large porous zeolite.
[0051] The mass fraction of titanium dioxide is 2% to 14%.
[0052] This invention also provides a method for preparing a catalyst based on BP25@ZEO-1, comprising the following steps:
[0053] Synthetic seed crystals: P25 was loaded onto ZEO-1 using the urea co-precipitation method to obtain P25 / ZEO-1 composite seed crystals;
[0054] The template agent was evenly dispersed in water, and silicon source, aluminum source, halide, P25 / ZEO-1 composite seed crystal and the remaining water were added. The mixture was stirred evenly to obtain a gel-like mixture.
[0055] The gel-like mixture was loaded into a hydrothermal synthesis reactor and reacted at 180~200℃ for 3~21 days. After washing and drying, P25@ZEO-1 material was obtained.
[0056] The BP25@ZEO-1 catalyst was obtained by mixing P25@ZEO-1 material with sodium borohydride, grinding and calcining.
[0057] Understandably, this specific implementation method first disperses the template agent and precisely mixes multiple raw materials to form a gel-like mixture, laying a uniform foundation for the subsequent material structure; then, a hydrothermal reaction at 180~200℃ for 3~21 days fully ensures the composite effect of P25 and ZEO-1. Combined with washing and drying, impurities can be removed to ensure the purity of P25@ZEO-1 material; finally, P25@ZEO-1 is mixed, ground, and calcined with sodium borohydride. The process is simple and easy to operate, which can achieve efficient modification of P25 to black titanium dioxide (BP25) and ensure stable encapsulation of BP25 in ZEO-1. The overall process does not require complex equipment, and the key parameters (temperature, time) are clearly defined, which is conducive to controlling the consistency of product quality. At the same time, no highly toxic or difficult-to-treat waste is generated, which is in line with the green preparation concept and provides a feasible and efficient path for the large-scale production of BP25@ZEO-1 catalyst.
[0058] Furthermore, the template agent is tricyclohexylmethylphosphine, prepared by the following method:
[0059] Tricyclohexylphosphine was reacted with iodomethane at room temperature for 2-5 days, followed by rotary evaporation and drying to obtain the template agent.
[0060] It is understandable that the molecular spatial configuration of tricyclohexylmethylphosphine consists of three cyclohexyl groups (a relatively large cyclic structure) and one methyl group (a small group). Its overall spatial size and three-dimensional configuration can serve as a molecular template to precisely fill the pore precursor structure of the zeolite crystal nucleus during the hydrothermal synthesis of ZEO-1 molecular sieves. This guides the zeolite crystals to grow in a specific direction, ultimately forming ultra-large pores that meet the encapsulation requirements of BP25 (particle size 10~20nm). Compared with traditional zeolite template agents (such as tetrapropylammonium hydroxide, which has a smaller molecular volume) that easily form microporous or mesoporous structures, the large volume characteristic of tricyclohexylmethylphosphine can directly determine the pore size of ZEO-1, avoiding the complex steps of subsequent pore expansion. This ensures that the pores can accommodate BP25 without clogging, while providing sufficient space for CO2 diffusion.
[0061] More preferably, in the P25 / ZEO-1 composite seed crystal, the molar ratio of P25 to ZEO-1 is 1:(3~7).
[0062] Understandably, compared to simply using a physical mixture of P25 and ZEO-1 as seed crystals, the integrated structure formed by the urea co-precipitation method using composite seed crystals allows for a tighter interfacial bond between P25 and ZEO-1 (rather than the loose contact of physical mixing). This enables P25 to be uniformly and stably anchored on the surface and near the pores of ZEO-1. In subsequent hydrothermal synthesis, P25 can serve as an active growth point to guide the directional growth of ZEO-1 crystals around P25, ensuring that P25 is precisely encapsulated rather than simply attached. At the same time, this tight bond avoids the problem of uneven dispersion of P25 and ZEO-1 due to density differences during physical mixing, reducing the risk of ZEO-1 pore blockage. Furthermore, the synergistic effect of composite seed crystals can further shorten the crystallization time of ZEO-1 and improve the regularity of the crystal structure. Ultimately, this provides the BP25@ZEO-1 catalyst with better dispersion of active components and a better support pore structure, significantly enhancing the stability and reproducibility of photocatalytic performance.
[0063] Furthermore, the ZEO-1 is a ZEO-1-Na type zeolite with a silica-alumina ratio of 25~50.
[0064] Furthermore, in the gel mixture, the molar ratio of silicon source: template agent: aluminum source: sodium chloride: P25 / ZEO-1 composite seed crystal is 1:0.5:0.04:0.01:0.01.
[0065] Furthermore, the P25 is a nanoscale mixed crystal titanium dioxide composed of anatase and rutile in a ratio of approximately 80:20, with a particle size of 10~20nm.
[0066] The present invention also provides an application of a BP25@ZEO-1-based catalyst, wherein the BP25@ZEO-1-based catalyst is used for photocatalytic reduction of CO from CO2.
[0067] Furthermore, the application of BP25@ZEO-1-based catalysts includes the following steps:
[0068] The BP25@ZEO-1-based catalyst was dissolved in ethanol, sonicated, and then dropped onto a quartz plate, air-dried, and placed into a photocatalytic reactor.
[0069] Add water dropwise into the photocatalytic reactor;
[0070] A gas containing CO2 is introduced into the photocatalytic reactor and then sealed.
[0071] Place the device under a xenon lamp for illumination;
[0072] The condensation process continues throughout.
[0073] Furthermore, based on the application of the BP25@ZEO-1 catalyst, the CO2-containing gas can be pure CO2 or a mixture of CO2 and N2 in different proportions.
[0074] Example 1
[0075] Synthesis of a 2%-BP25@ZEO-1-Na type catalyst
[0076] S1. Disperse 2 mmol P25 and 10 mmol ZEO-1 molecular sieves in 50 mL of deionized water, dissolve 50 mmol urea in 50 mL of deionized water, mix the two solutions and seal, stir at 90 °C for 6 h, centrifuge, dry, and obtain 2%-BP / ZEO-1 seed crystals.
[0077] S2, 2.9 g of tricyclohexylphosphine, and 5 mL of iodomethane were reacted at room temperature for 3 days, followed by rotary evaporation and drying. The template agent was obtained.
[0078] S3. The synthesized template agent was uniformly dispersed in water, and 0.081 g aluminum isopropoxide, 2.25 mL tetraethyl orthosilicate, 0.03 g seed crystals, 0.053 g sodium chloride, and 1.8 g water were added sequentially. The mixture was placed in a hydrothermal reactor and reacted at 190 °C for 3 days. After centrifugation, washing with water, and drying, P25@ZEO-1 was obtained.
[0079] S4. Under an argon atmosphere, P25@ZEO-1 obtained in S3 and sodium borohydride were calcined at a mass ratio of 1:1 and reacted at 400°C for 1 hour. The product was removed, washed alternately with hydrochloric acid and ethanol, and dried. The final product was obtained.
[0080] Example 2
[0081] Synthesis of a 2%-BP@ZEO-1-H type catalyst
[0082] In Example 1, step S3 involves replacing 0.053g of sodium chloride with 180µL of 40% hydrochloric acid. Additionally, the hydrothermal reactor time is extended from 3 days to 21 days. The remaining steps remain unchanged.
[0083] Example 3
[0084] Synthesis of a BP@ZEO-1-Na type catalyst encapsulated in different ratios
[0085] Adding 2 mmol of P25 to step S1 in Example 1 can be replaced with 6, 8, 10, or 14 mmol. The remaining steps remain unchanged.
[0086] Example 4
[0087] Synthesis of a catalyst encapsulated with 2%-BP@ZEO-1-Na with different silicon-to-aluminum ratios
[0088] In step S3 of Example 1, the silicon-to-aluminum ratio can be expanded from the original 25 to 50. The remaining steps remain unchanged.
[0089] A method for photocatalytic reduction of CO2 to CO using a BP@ZEO-1 catalyst encapsulated in the catalyst includes the following steps:
[0090] S1. Disperse 1 mg of catalyst in 500 μL of ethanol;
[0091] S2. Evenly drop the prepared dispersion onto a quartz plate, place it in a gas-solid reactor, and add 100 microliters of water.
[0092] S3. Introduce CO2 gas into the reactor for 30 minutes to saturate it;
[0093] S4. Take samples every hour and analyze the products using gas chromatography.
[0094] Physical characterization:
[0095] like Figure 1 As shown, based on test or comparative experimental data, this invention prepared XRD patterns for the black titanium dioxide@zeolite catalyst. Compared with the original ZEO-1 pattern, the crystallinity of the encapsulated molecular sieve decreased, but the basic diffraction peak positions remained unchanged, indicating that the structure of ZEO-1 remained stable after encapsulation. Furthermore, a titanium dioxide peak appeared at 48°, indicating successful composite formation.
[0096] like Figure 2 As shown, the diffraction peaks of the solid Si NMR of the black titanium dioxide@zeolite material are weaker than those of the original zeolite spectrum, indicating that some silanols inside the molecular sieve were consumed and used to connect titanium dioxide to form Si-O-Ti bonds, which indirectly proves that titanium dioxide was successfully encapsulated inside the zeolite.
[0097] like Figure 3 As shown, the N2 adsorption isotherm of the black titanium dioxide@zeolite material was measured. The results indicate that introducing titanium dioxide into the zeolite disrupts the original pore structure, leading to a decrease in adsorption capacity. This indirectly proves the feasibility of the synthesis strategy.
[0098] The above description is merely a preferred embodiment of the present invention and is not intended to limit the present invention in any way. Although the present invention has been shown above with preferred embodiments, it is not intended to limit the present invention. Any person skilled in the art can make some modifications or alterations to the above-disclosed technical content to create equivalent embodiments without departing from the scope of the present invention. Any simple modifications, equivalent changes and alterations made to the above embodiments based on the technical essence of the present invention without departing from the scope of the present invention shall still fall within the scope of the present invention.
Claims
1. A catalyst based on BP25@ZEO-1, characterized in that, The catalyst based on BP25@ZEO-1 is a catalyst of black titanium dioxide encapsulated in ultraporous zeolite. The mass fraction of titanium dioxide is 2% to 14%.
2. The method for preparing the BP25@ZEO-1-based catalyst according to claim 1, characterized in that, Includes the following steps: Synthetic seed crystals: P25 was loaded onto ZEO-1 using the urea co-precipitation method to obtain P25 / ZEO-1 composite seed crystals; The template agent was evenly dispersed in water, and silicon source, aluminum source, halide, P25 / ZEO-1 composite seed crystal and the remaining water were added. The mixture was stirred evenly to obtain a gel-like mixture. The gel-like mixture was loaded into a hydrothermal synthesis reactor and reacted at 180~200℃ for 3~21 days. After washing and drying, P25@ZEO-1 material was obtained. The BP25@ZEO-1 catalyst was obtained by mixing P25@ZEO-1 material with sodium borohydride, grinding and calcining.
3. The method for preparing the BP25@ZEO-1-based catalyst according to claim 1, characterized in that, The template agent is tricyclohexylmethylphosphine, prepared by the following method: Tricyclohexylphosphine was reacted with iodomethane at room temperature for 2-5 days, followed by rotary evaporation and drying to obtain the template agent.
4. The method for preparing the BP25@ZEO-1-based catalyst according to claim 2 or 3, characterized in that, In the P25 / ZEO-1 composite seed crystal, the molar ratio of P25 to ZEO-1 is 1:(3~7).
5. The method for preparing the BP25@ZEO-1-based catalyst according to claim 4, characterized in that, The ZEO-1 is a ZEO-1-Na type zeolite with a silica-alumina ratio of 25~50.
6. The method for preparing the BP25@ZEO-1-based catalyst according to claim 1, characterized in that, In the gel mixture, the molar ratio of silicon source: template agent: aluminum source: sodium chloride: P25 / ZEO-1 composite seed crystal is 1:0.5:0.04:0.01:0.
01.
7. The method for preparing the BP25@ZEO-1-based catalyst according to claim 4, characterized in that, The P25 is a nanoscale mixed crystal titanium dioxide composed of anatase and rutile in a ratio of approximately 80:20, with a particle size of 10~20nm.
8. The application of the BP25@ZEO-1-based catalyst according to claim 1, characterized in that, The BP25@ZEO-1-based catalyst is used for photocatalytic CO2 reduction of CO.
9. The application according to claim 8, characterized in that, Includes the following steps: The BP25@ZEO-1-based catalyst was dissolved in ethanol, sonicated, and then dropped onto a quartz plate, air-dried, and placed into a photocatalytic reactor. Add water dropwise into the photocatalytic reactor; A gas containing CO2 is introduced into the photocatalytic reactor and then sealed. Place the device under a xenon lamp for illumination; The condensation process continues throughout.
10. The application according to claim 9, characterized in that, The gas containing CO2 can be pure CO2 or a mixture of CO2 and N2 in different proportions.