Functionalized hydrogen bond organic framework photocatalyst induced by high-energy electron beam irradiation as well as preparation method and application of functionalized hydrogen bond organic framework photocatalyst

Abstract

The invention discloses a preparation method and application of a functional hydrogen bond organic framework photocatalyst induced by high-energy electron beam irradiation, and belongs to the technical field of novel environmental catalysis materials.The preparation method comprises the steps that zinc salt and a hydrogen bond organic framework are added into an isopropanol solution, stirred to be uniform and sealed, N2 is introduced, the mixed solution is irradiated through high-energy electron beam irradiation, and the photocatalyst is obtained; and centrifugally cleaning the mixed solution subjected to high-energy electron beam irradiation with ethanol to obtain the high-energy electron beam irradiation induced functionalized hydrogen bond organic framework catalyst. The preparation method of the functionalized hydrogen bond organic framework catalyst induced by high-energy electron beam irradiation, provided by the invention, has the advantages of relatively simple operation, low cost, large-scale preparation and the like; the high-energy electron beam irradiation induced functionalized hydrogen bond organic framework catalyst prepared by the invention has excellent performance of photocatalytic reduction of CO2 into CO under full spectrum and CO2 atmosphere.

Description

TECHNICAL FIELD

[0001] The application belongs to the technical field of new environmental catalytic materials, and particularly relates to a high-energy electron beam irradiation-induced functionalized hydrogen-bonded organic framework photocatalyst and a preparation method and application thereof. BACKGROUND

[0002] With the large consumption of fossil energy and the aggravation of global climate change, the concentration of carbon dioxide in the atmosphere continues to rise, causing greenhouse effect and ecological environment deterioration. The efficient conversion and resource utilization of carbon dioxide have become the core challenge in the field of energy and environment. The photocatalytic reduction of carbon dioxide has attracted widespread attention because it is driven by solar energy, has mild reaction conditions and a green and clean process. This technology can reduce carbon dioxide to carbon monoxide, methane, methanol and other high-value carbon resources, and has important significance in building a carbon neutral energy cycle system. However, the existing photocatalysts still have bottlenecks in reduction efficiency, selectivity and stability, which restricts their large-scale application. Developing new photocatalytic materials with high specific surface area, rich active sites and excellent light response performance is the key to improving the efficiency of CO2 photocatalytic reduction.

[0003] Hydrogen-bonded organic framework (HOFs) is a kind of porous crystalline material constructed by hydrogen bonding as the main connection mode, which has the advantages of strong structure designability, large specific surface area and high crystallinity. However, HOFs often lack effective electron transfer channels and active centers, which limits the performance of photocatalysis. In recent years, functional modification has become the main way to improve the catalytic activity of HOFs, among which the introduction of heteroatoms, defect structures or metal sites can effectively enhance the light absorption capacity and carrier separation efficiency. High-energy electron beam irradiation technology is a clean physical modification method without high temperature and high pressure, which can precisely control the microstructure and chemical environment by irradiation-induced bond breaking, crosslinking or doping while maintaining the macrostructure of the material. Applying electron beam irradiation to the functionalization of HOFs can not only construct stable and efficient catalytic active centers, but also enhance the framework stability and electron transport capacity, showing broad development prospects in the field of photocatalytic CO2 reduction. However, there is still a lack of electron beam functionalization modification methods for HOFs and systematic research on their application in CO2 photocatalytic reduction. Therefore, it is urgent to develop an efficient, green and controllable electron beam-induced HOFs functionalization strategy to construct a new photocatalyst system and promote the development of CO2 resource conversion technology. SUMMARY

[0004] The purpose of the present application is to provide a high-energy electron beam irradiation-induced functionalized hydrogen-bonded organic framework photocatalyst and a preparation method and application thereof to solve the problems existing in the prior art.

[0005] One of the technical solutions provided by the present application is:

[0006] A high-energy electron beam irradiation induced functionalized hydrogen-bonded organic framework photocatalyst, a preparation method thereof and an application thereof, which is prepared by treating an isopropanol solution containing a zinc salt and a hydrogen-bonded organic framework (HOF-BTPA) with high-energy electron beam irradiation.

[0007] The second technical solution provided by the present application is:

[0008] A preparation method of the high-energy electron beam irradiation induced functionalized hydrogen-bonded organic framework photocatalyst, comprising the following steps: adding a zinc salt solution and a hydrogen-bonded organic framework (HOF-BTPA) into an isopropanol solution, stirring uniformly, sealing and then introducing N2, irradiating the mixed solution with high-energy electron beam, cleaning the mixed solution irradiated with high-energy electron beam with ethanol, centrifuging, and obtaining the high-energy electron beam irradiation induced functionalized hydrogen-bonded organic framework photocatalyst.

[0009] The mass-volume ratio of the zinc salt solution and the hydrogen-bonded organic framework is 5mL:15mg.

[0010] The zinc salt in the zinc salt solution is zinc nitrate; and the concentration of the zinc salt solution is 0.05-0.2M.

[0011] The mass-volume ratio of the hydrogen-bonded organic framework (HOF-BTPA) and isopropanol is 15mg:10mL.

[0012] The high-energy electron beam irradiation is in the form of 15KGy / round and the irradiation dose is 60-180KGy.

[0013] High-energy electron beam irradiation is a technology that changes the performance of materials through the interaction of high-energy electrons and matter. Electron beam irradiation can induce the ionization or excitation of material molecules, thereby releasing orbital electrons and forming active species such as free radicals, which promote the reconstruction of the original molecular structure. This process not only destroys the original chemical bonds, but also promotes the occurrence of new chemical reactions, thereby optimizing the performance of materials.

[0014] In the present application, high-energy electron beams excite the decomposition of zinc nitrate to release zinc ions (Zn 2+ ) and induce the radiolysis of solvent molecules to produce highly active free radicals (such as OH•, H•). These free radicals further promote the combination of Zn 2+ and active sites in HOFs (such as hydrogen bond donor / acceptor units, carboxyl groups). Zn 2+ is firmly combined with HOFs through electrostatic interaction, coordination bond and hydrogen bond induction effect, giving it a stable functionalized structure. At the same time, the radiative effect of high-energy electron beams may also induce the adjustment of the microstructure of HOFs, optimizing the pore environment of HOFs for Zn2+ The introduction of Zn provides more ideal physical and chemical conditions. 2+ The introduction of Zn can change the electronic structure of HOFs, reduce the band gap, enhance the light absorption capacity, promote the charge separation and transmission efficiency, and has potential application value in the field of photocatalysis. Compared with the traditional chemical functionalization method, high-energy electron beam irradiation has the advantages of green environmental protection, efficient reaction, uniform distribution and the like, and provides a new fast and efficient way for the preparation of functionalized HOFs.

[0015] The third technical solution provided by the application is:

[0016] The application of the functionalized hydrogen-bonded organic framework photocatalyst induced by high-energy electron beam irradiation in photocatalytic energy conversion.

[0017] The energy conversion is used for photocatalytic conversion of CO2 into CO.

[0018] Compared with the prior art, the application has the following advantages and technical effects:

[0019] The preparation method of the functionalized hydrogen-bonded organic framework photocatalyst induced by high-energy electron beam irradiation has the advantages of relatively simple operation, low cost, and mass production; and the functionalized hydrogen-bonded organic framework photocatalyst prepared by the application can selectively convert CO2 into CO through photocatalytic effect.

[0020] Compared with the traditional magnetic stirring method, the functionalized hydrogen-bonded organic framework photocatalyst prepared by the application has better photocatalytic performance under the same conditions of the reaction system, and has more excellent reduction effect on CO2 under visible light, which proves that the irradiation modification effect is better, and overcomes the defects in the prior art. Compared with the traditional functionalization method, the application uses high-energy electron beam irradiation, which irradiates the substance with accelerated electrons in a high-voltage electric field, rapidly and uniformly heats the reaction system, and causes the interaction between high-energy electrons and the substance, so as to ionize and excite the molecules of various substances, initiate chemical reactions, and improve the performance of the material. Therefore, the reaction has the characteristics of fast reaction speed, high energy utilization rate, sensitive reaction, short synthesis time, high efficiency, energy saving, green environmental protection and the like. BRIEF DESCRIPTION OF DRAWINGS

[0021] In order to more clearly illustrate the technical solutions in the embodiments of the application or the prior art, the drawings needed in the embodiments will be briefly introduced below. Obviously, the drawings in the following description are only some embodiments of the application, and other drawings can be obtained by those skilled in the art without creative labor.

[0022] Figure 1 XRD pattern of the functionalized hydrogen bonded organic framework photocatalyst prepared for Example 1-5;

[0023] Figure 2 SEM image of the functionalized hydrogen bonded organic framework photocatalyst prepared for Example 2;

[0024] Figure 3 Comparison of the reduction of CO2 under full spectrum for the functionalized hydrogen bonded organic framework photocatalysts prepared for Examples 1-3;

[0025] Figure 4 Comparison of the reduction of CO2 under full spectrum for the functionalized hydrogen bonded organic framework photocatalysts prepared for Examples 2 and 4-5;

[0026] Figure 5 Comparison of the reduction of CO2 under full spectrum for Zn-HOF (0.1 M, 120 kGy) prepared for Example 2 and Zn-HOF (SM) prepared for Comparative Example 1. DETAILED DESCRIPTION

[0027] Various illustrative embodiments of the present application are now described in detail below. The following description includes specific details for the purpose of providing a thorough understanding of the present application. However, it will be apparent to those skilled in the art that the present application can be practiced without these specific details. In some instances, well-known structures and functions have not been described in detail in order to avoid obscuring the concept of the present application.

[0028] It is to be understood that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the present application. In addition, for a range of values of a parameter, unless otherwise stated, the inclusion of either extremity of the range is to be understood as if both are mentioned. Likewise, for a parameter declared to be "one of", "any one of" or "one selected from the group consisting of" a multitude of alternatives, this is to be understood to mean any one of said alternatives individually or, where the context permits, several of said alternatives taken together. Furthermore, where "comprising" is used in the description or claims, it is to be understood that other embodiments can also consist of "consisting only of", or "consisting essentially of", the listed steps or components.

[0029] Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application belongs. Although any methods and materials similar or equivalent to those described herein can be used in the practice or testing of the present application, the preferred methods and materials are described. All patents, patent applications, publications, and descriptions mentioned herein are incorporated by reference to the extent allowed by law. In the case of conflict between the description herein and the incorporated material, the description shall control.

[0030] Various modifications and variations can be made to the specific embodiments described in this specification without departing from the scope or spirit of the invention, as will be apparent to those skilled in the art. Other embodiments derived from this specification will also be apparent to those skilled in the art. This specification and embodiments are merely exemplary.

[0031] The terms “include,” “including,” “have,” “contain,” etc., used in this article are all open-ended terms, meaning that they include but are not limited to.

[0032] Compared to the commonly used, slow magnetic stirring method, irradiation-induced polymerization (IRP) is a highly efficient material modification technique. It allows for direct application of high-energy rays to substances under ambient temperature and pressure, or specific conditions, initiating internal chemical reactions that alter the material's structure and properties. This results in a highly efficient, energy-saving, and environmentally friendly synthesis process. Applying IRP to the preparation of HOF-functionalized photocatalysts holds promise for achieving precise control over the structure and properties of HOF materials by adjusting irradiation conditions and material dosage, further enhancing their stability and functionalization level. Furthermore, this method is not only simple to operate and allows for precise control of reaction conditions and product properties, but also typically produces materials with high purity, good dispersibility, and excellent performance.

[0033] This invention provides a high-energy electron beam irradiation-induced functionalized hydrogen-bonded organic framework photocatalyst, which is prepared by treating an isopropanol solution containing zinc salt and hydrogen-bonded organic framework with high-energy electron beam irradiation.

[0034] This invention also provides a method for preparing the above-mentioned high-energy electron beam irradiation-induced functionalized hydrogen-bonded organic framework photocatalyst, comprising the following steps: adding a zinc salt solution and a hydrogen-bonded organic framework to an isopropanol solution, stirring evenly, sealing and then introducing N2, irradiating the mixed solution with a high-energy electron beam, washing the mixed solution after high-energy electron beam irradiation with ethanol, centrifuging, and obtaining the high-energy electron beam irradiation-induced functionalized hydrogen-bonded organic framework photocatalyst.

[0035] In the following embodiments of the present invention, the mass-to-volume ratio of the zinc salt solution and the hydrogen-bonded organic framework is 5 mL: 15 mg.

[0036] In an embodiment of the present invention, the zinc salt in the zinc salt solution is zinc nitrate; the concentration of the zinc salt solution is 0.05~0.2M.

[0037] In an embodiment of the present invention, the mass-to-volume ratio of the hydrogen-bonded organic framework (HOF-BTPA) to isopropanol is 15 mg: 10 mL.

[0038] In an embodiment of the present invention, the high-energy electron beam irradiation is performed at a rate of 15 KGy / cycle to irradiate 60~180 KGy.

[0039] This invention also provides the application of the high-energy electron beam irradiation-induced functionalized hydrogen-bonded organic framework photocatalyst in photocatalytic energy conversion, wherein the energy is converted into CO2 and then into CO.

[0040] The preparation method of hydrogen-bonded organic framework (HOF-BTPA) in this embodiment of the invention is as follows: 0.177 g of 4'-(4-carboxyphenyl)-2,2':6',2''-terpyridine (BTPA), 6 mL of deionized water, 4 mL of dimethylformamide solution (DMF), and 200 μL of concentrated nitric acid are mixed and added to a 25 mL silicone-lined screw-cap bottle. The mixture is ultrasonically treated for 5 min to obtain a uniform milky white solution. Subsequently, the solution is transferred to an oven and kept at 100 °C for 72 h. After cooling to room temperature, it is washed three times by centrifugation with ethanol and dried in a fume hood for 12 h to obtain colorless powder crystals, which is HOF-BTPA.

[0041] Example 1

[0042] A method for preparing a high-energy electron beam irradiation-induced functionalized hydrogen-bonded organic framework photocatalyst:

[0043] 1) Prepare a 0.05M zinc nitrate solution and sonicate it thoroughly.

[0044] 2) Disperse 15 mg of HOF-BTPA crystals and 5 mL of 0.05 M zinc nitrate solution into 10 mL of isopropanol, and sonicate thoroughly to obtain a mixed solution;

[0045] 3) Place the mixed solution in a sealed irradiation container, introduce high-purity N2, and then completely expel the air;

[0046] 4) Irradiate the sealed container filled with N2 in step 3) with a high-energy electron beam at a rate of 15 KGy / cycle to a total of 120 KGy;

[0047] 5) Centrifuge the mixed solution after high-energy electron beam irradiation in step 4) at 6000 rpm for 5 min, remove the supernatant, add ethanol to wash and repeat centrifugation 3 times, collect the bottom product, dry it to obtain the high-energy electron beam irradiation induced functionalized hydrogen bond organic framework material, labeled as Zn-HOF (0.05M, 120kGy).

[0048] Example 2

[0049] A method for preparing high-energy electron beam irradiation-induced functionalized hydrogen-bonded organic framework materials:

[0050] 1) Prepare a 0.1M zinc nitrate solution and sonicate it thoroughly.

[0051] 2) Disperse 15 mg of HOF-BTPA crystals and 5 mL of 0.1 M zinc nitrate solution into 10 mL of isopropanol, and sonicate thoroughly to obtain a mixed solution;

[0052] 3) Place the mixed solution in a sealed irradiation container, introduce high-purity N2, and then completely expel the air;

[0053] 4) Irradiate the sealed container filled with N2 in step 3) with a high-energy electron beam at a rate of 15 KGy / cycle to a total of 120 KGy;

[0054] 5) Centrifuge the mixed solution after high-energy electron beam irradiation in step 4) at 6000 rpm for 5 min, remove the supernatant, add ethanol to wash and repeat centrifugation 3 times, collect the bottom product, dry it to obtain the high-energy electron beam irradiation induced functionalized hydrogen bond organic framework material, labeled as Zn-HOF (0.1M, 120kGy).

[0055] Example 3

[0056] A method for preparing high-energy electron beam irradiation-induced functionalized hydrogen-bonded organic framework materials:

[0057] 1) Prepare a 0.2M zinc nitrate solution and sonicate it thoroughly.

[0058] 2) Disperse 15 mg of HOF-BTPA crystals and 5 mL of 0.2 M zinc nitrate solution into 10 mL of isopropanol, and sonicate thoroughly to obtain a mixed solution;

[0059] 3) Place the mixed solution in a sealed irradiation container, introduce high-purity N2, and then completely expel the air;

[0060] 4) Irradiate the sealed container filled with N2 in step 3) with a high-energy electron beam at a rate of 15 KGy / cycle to a total of 120 KGy;

[0061] 5) Centrifuge the mixed solution after high-energy electron beam irradiation in step 4) at 6000 rpm for 5 min, remove the supernatant, add ethanol to wash and repeat centrifugation 3 times, collect the bottom product, dry it to obtain the high-energy electron beam irradiation induced functionalized hydrogen bond organic framework material, labeled as Zn-BTPA (0.2M, 120kGy).

[0062] Example 4

[0063] A method for preparing high-energy electron beam irradiation-induced functionalized hydrogen-bonded organic framework materials:

[0064] 1) Prepare a 0.1M zinc nitrate solution and sonicate it thoroughly.

[0065] 2) Disperse 15 mg of HOF-BTPA crystals and 5 mL of 0.1 M zinc nitrate solution into 10 mL of isopropanol, and sonicate thoroughly to obtain a mixed solution;

[0066] 3) Place the mixed solution in a sealed irradiation container, introduce high-purity N2, and then completely expel the air;

[0067] 4) Irradiate the sealed container filled with N2 in step 3) with a high-energy electron beam at a rate of 15 KGy / cycle to a total of 60 KGy;

[0068] 5) Centrifuge the mixed solution after high-energy electron beam irradiation in step 4) at 6000 rpm for 5 min, remove the supernatant, add ethanol to wash and repeat centrifugation 3 times, collect the bottom product, dry it to obtain the high-energy electron beam irradiation induced functionalized hydrogen bond organic framework material, labeled as Zn-BTPA (0.1M, 60kGy).

[0069] Example 5

[0070] A method for preparing high-energy electron beam irradiation-induced functionalized hydrogen-bonded organic framework materials:

[0071] 1) Prepare a 0.1M zinc nitrate solution and sonicate it thoroughly.

[0072] 2) Disperse 15 mg of HOF-BTPA crystals and 5 mL of 0.1 M zinc nitrate solution into 10 mL of isopropanol, and sonicate thoroughly to obtain a mixed solution;

[0073] 3) Place the mixed solution in a sealed irradiation container, introduce high-purity N2, and then completely expel the air;

[0074] 4) Irradiate the sealed container filled with N2 in step 3) with a high-energy electron beam at a rate of 15 KGy / cycle to 180 KGy;

[0075] 5) Centrifuge the mixed solution after high-energy electron beam irradiation in step 4) at 6000 rpm for 5 min, remove the supernatant, add ethanol to wash and repeat centrifugation 3 times, collect the bottom product, dry it to obtain the high-energy electron beam irradiation induced functionalized hydrogen bond organic framework material, labeled as Zn-BTPA (0.1M, 180kGy).

[0076] Comparative Example 1

[0077] Preparation method of functionalized hydrogen-bonded organic framework materials by magnetic stirring

[0078] 1) Prepare a 0.1M zinc nitrate solution and sonicate it thoroughly.

[0079] 2) Disperse 15 mg of HOF-BTPA crystals and 5 mL of 0.1 M zinc nitrate solution into 10 mL of isopropanol, and sonicate thoroughly to obtain a mixed solution;

[0080] 3) Place the mixed solution in a sealed irradiation container, introduce high-purity N2, and then completely expel the air;

[0081] 4) Stir the mixture from step 3) magnetically for 24 hours;

[0082] 5) Centrifuge the mixed solution after magnetic stirring in step 4) at 6000 rpm for 5 min, remove the supernatant, add ethanol to wash and repeat the centrifugation 3 times, collect the bottom product, dry it to obtain the magnetic stirring induced functionalized hydrogen bond organic framework material, labeled as Zn-BTPA (SM).

[0083] Figure 1 XRD patterns of the functionalized hydrogen-bonded organic framework photocatalysts prepared in Examples 1-5;

[0084] Figure 2 SEM image of the functionalized hydrogen-bonded organic framework photocatalyst prepared in Example 2;

[0085] Figure 3 The graph shows a comparison of the CO2 reduction effects of the functionalized hydrogen-bonded organic framework photocatalysts prepared in Examples 1-3 under the full spectrum.

[0086] Figure 4 The graph shows a comparison of the CO2 reduction effects of the functionalized hydrogen-bonded organic framework photocatalysts prepared in Examples 2 and 4-5 under the full spectrum.

[0087] Figure 5 A comparison of the reduction effects of Zn-HOF (0.1M, 120kGy) prepared in Example 2 and Zn-HOF (SM) prepared in Comparative Example 1 on CO2 reduction under the full spectrum;

[0088] Figure 1 The XRD diffraction peak positions of the high-energy electron beam irradiation-induced functionalized hydrogen-bonded organic framework photocatalysts Zn-HOF (0.1M, 120kGy), Zn-HOF (0.1M, 60kGy), Zn-HOF (0.1M, 180kGy), Zn-HOF (0.05M, 120kGy) and Zn-HOF (0.2M, 120kGy) prepared according to the present invention showed basically no shift and no other impurities were generated. This indicates that the framework of the high-energy electron beam irradiation-induced functionalized hydrogen-bonded organic framework photocatalysts prepared according to the present invention has not been changed or caused crystal structure collapse.Figure 2 This invention demonstrates that the high-energy electron beam irradiation-induced functionalized hydrogen-bonded organic framework photocatalyst prepared by this invention has a uniform Zn distribution.

[0089] 10 mg of photocatalysts prepared in different examples and comparative examples were weighed and dispersed on a ceramic crucible with 1 mL of deionized water. After ultrasonic homogenization, the crucible was placed in a 40°C oven for 2 hours to form a film. A mixed solution of 5 mL triethanolamine and 4.5 mL deionized water was added to a quartz reactor. The ceramic crucible containing the photocatalyst was placed on top, suspended in the air. After sealing, N2 was continuously introduced to purge excess air from the reactor, followed by continuous introduction of high-purity CO2 to ensure that only CO2 existed in the reaction system. Circulating water was introduced, and a xenon lamp (300W xenon lamp) was turned on. A sample was taken every hour, three times each time, and the average value was taken. The product was detected using gas chromatography, and the yield was calculated. Thus, the photocatalytic reduction efficiency of the photocatalyst for CO2 was calculated.

[0090] from Figures 3-5 As can be seen from the above, the photocatalysts Zn-HOF (0.1M, 120kGy), Zn-HOF (0.1M, 60kGy), Zn-HOF (0.1M, 180kGy), Zn-HOF (0.05M, 120kGy), and Zn-HOF (0.2M, 120kGy) prepared in this invention exhibit the best performance in photocatalytic reduction of CO2 under full-spectrum conditions. It is evident that differences in irradiation dose and zinc salt concentration affect the performance of the prepared functionalized hydrogen-bonded organic framework photocatalysts. Among them, the photocatalyst Zn-HOF (0.1M, 120kGy) demonstrates the most excellent performance in photocatalytic reduction of CO2.

[0091] Figure 5 It can be seen that the high-energy electron beam irradiation-induced functionalized hydrogen-bonded organic framework photocatalyst Zn-HOF (0.1M, 120kGy) can achieve 8.5 times the performance of photocatalytic reduction of CO2 as the magnetically stirred photocatalyst Zn-HOF (SM).

[0092] The above are merely preferred embodiments of the present invention, but the scope of protection of the present invention is not limited thereto. Any variations or substitutions that can be easily conceived by those skilled in the art within the scope of the technology disclosed in the present invention should be included within the scope of protection of the present invention. Therefore, the scope of protection of the present invention should be determined by the scope of the claims.

Claims

1. A high-energy electron beam irradiation-induced functionalized hydrogen-bonded organic framework photocatalyst, characterized in that, The isopropanol solution containing a zinc salt and a hydrogen-bonded organic framework is subjected to high-energy electron beam irradiation treatment.

2. A method for the preparation of the high-energy electron beam irradiation-induced functionalized hydrogen-bonded organic framework photocatalyst according to claim 1, characterized in that, The method comprises the following steps: adding a zinc salt solution and a hydrogen-bonded organic framework into an isopropanol solution, stirring uniformly, sealing and introducing N2, irradiating the mixed solution by high-energy electron beam irradiation, and centrifugally cleaning the mixed solution after high-energy electron beam irradiation with ethanol to obtain the high-energy electron beam irradiation-induced functionalized hydrogen-bonded organic framework photocatalyst.

3. The method for the preparation of high-energy electron beam irradiation induced functionalized hydrogen-bonded organic framework photocatalysts according to claim 2, characterized in that, The mass-volume ratio of the hydrogen-bonded organic framework to the zinc salt solution is 15 mg:5 mL.

4. The method for the preparation of high-energy electron beam irradiation induced functionalized hydrogen-bonded organic framework photocatalysts according to claim 2, characterized in that, The zinc salt in the zinc salt solution is zinc nitrate; and the concentration of the zinc salt solution is 0.05-0.2 M.

5. The method for preparing a high-energy electron beam irradiation-induced functionalized hydrogen-bonded organic framework photocatalyst according to claim 2, characterized in that, The mass-volume ratio of the hydrogen-bonded organic framework to isopropanol is 15 mg:10 mL.

6. The method for the preparation of high-energy electron beam irradiation induced functionalized hydrogen-bonded organic framework photocatalysts according to claim 2, characterized in that, The high-energy electron beam irradiation is in the form of 15 KGy / round and is irradiated to 60-180 KGy.

7. A high-energy electron beam irradiation-induced functionalized hydrogen-bonded organic framework photocatalyst, characterized in that, The method is prepared according to any one of claims 1-6. 8.The high-energy electron beam irradiation-induced functionalized hydrogen-bonded organic framework photocatalyst of claim 7 is applied to photocatalytic energy conversion.

9. Use according to claim 7, characterized in that, The photocatalytic energy conversion is used for photocatalytic conversion of CO2 into CO, and is carried out under full spectrum.

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