Hydrogen bond framework nanotrap material, method of making and carbon capture applications thereof
By preparing the hydrogen-bonded framework nanotrap material HOF-Cu-DAP-SO4, and utilizing the one-dimensional pore structure formed by the interaction of metal salts, organic ligands and inorganic anions, the problem of insufficient adsorption selectivity and stability of existing carbon trapping materials was solved, and efficient CO2 capture and separation was achieved.
Patent Information
- Application Number
- CN202610127234.5
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2026-01-29
- Publication Date
- 2026-11-06
AI Technical Summary
Existing carbon capture materials have shortcomings in adsorption selectivity and stability, and their preparation costs are high, which limits their large-scale application.
By preparing the hydrogen-bonded framework nanotrap material HOF-Cu-DAP-SO4, a stable one-dimensional pore structure is formed by utilizing the interaction between metal salts, organic ligands and inorganic anions, thus constructing a "nanotrap" to improve the adsorption capacity and selectivity of CO2.
This material is easy to prepare at room temperature, has a high specific surface area and regular pores, and can efficiently adsorb CO2, especially exhibiting extremely high selectivity for CO2 in mixed gases. It is suitable for carbon dioxide capture in industrial waste gas and biogas purification.
Smart Images
Figure CN123038787A_ABST
Abstract
Description
Technical Field
[0001] This invention relates to the field of carbon capture technology, specifically to a hydrogen-bonded framework nanotrap material, its preparation method, and its carbon capture applications. Background Technology
[0002] The massive use of fossil fuels has led to a sharp rise in atmospheric carbon dioxide (CO2) concentrations, triggering a series of severe environmental problems, including global warming. Carbon capture, utilization, and storage (CCUS) technology, as an effective means of reducing atmospheric CO2 levels, has attracted widespread attention. Among carbon capture technologies, adsorption is considered one of the most promising technologies due to its advantages such as simple operation, low energy consumption, and low equipment investment.
[0003] Currently, there are many types of adsorbents used for carbon capture, including activated carbon, molecular sieves, and metal-organic frameworks (MOFs). Activated carbon has a large specific surface area and abundant pore structure, but its adsorption selectivity for CO2 is low; although molecular sieves have some adsorption selectivity for CO2, their adsorption capacity is limited and their regeneration energy consumption is high; MOFs have high specific surface area and tunable pore structure, exhibiting good adsorption performance for CO2, but their synthesis cost is high and their stability is poor, limiting their large-scale application.
[0004] Therefore, developing novel adsorbents with high adsorption capacity, high selectivity, good stability, and low cost is a current research hotspot and key challenge in the field of carbon capture. Hydrogen-bonded framework materials (HOFs), as a new type of porous material, form a three-dimensional framework structure through intermolecular hydrogen bonding interactions. They have advantages such as simple synthesis methods, strong structural designability, high porosity, and large specific surface area, showing great application potential in the field of gas adsorption and separation. However, most HOF materials currently have large particle sizes, making it difficult to fully utilize their internal pores, thus affecting their CO2 adsorption performance. Preparing HOFs into nanoscale materials and constructing nanomaterials with special trap structures is expected to further improve their CO2 adsorption capacity and selectivity, but related research reports are limited. Summary of the Invention
[0005] The purpose of this invention is to provide a hydrogen-bonded framework nanotrap material, its preparation method, and its carbon capture application, so as to solve the problems mentioned in the background art.
[0006] To achieve the above objectives, the embodiments of the present invention provide the following technical solutions:
[0007] A method for preparing a hydrogen-bonded framework nanotrap material includes the following steps:
[0008] 1) Dissolve CuSO4·5H2O in deionized water to form solution A;
[0009] 2) Add 2,6-diaminopurine to a mixed solvent consisting of N,N-dimethylacetamide and deionized water to form solution B;
[0010] 3) Add solution A dropwise to solution B while continuously stirring to allow the reaction to proceed;
[0011] 4) After the stirring reaction is completed, centrifugation is performed to obtain the precipitate. The precipitate is washed, and the washed product is dried under vacuum to obtain the hydrogen-bonded framework nanotrap material HOF-Cu-DAP-SO4.
[0012] As a preferred embodiment, in step 1), the ratio of CuSO4·5H2O to deionized water is 80-100 mg: 2-2.5 mL.
[0013] As a more preferred embodiment, in step 2), the dosage relationship of 2,6-diaminopurine, N,N-dimethylacetamide and deionized water is 43.6-54.5 mg: 10-12 mL: 3-3.6 mL.
[0014] As a more preferred option, in step 3), the dropping rate is 1-2 drops per second, the stirring reaction time is 48-72 hours, and the reaction temperature is room temperature.
[0015] As a more preferred embodiment, in step 4), the vacuum drying is performed at a temperature of 333K for 12-24 hours.
[0016] As a more preferred embodiment, in step 4), the precipitate is washed sequentially with N,N-dimethylformamide, deionized water, and methanol.
[0017] As a more preferred option, in step 4), centrifugation is performed after each washing.
[0018] This invention also provides a hydrogen-bonded framework nanotrap material, which is prepared by the above-described method for preparing hydrogen-bonded framework nanotrap materials.
[0019] The embodiments of the invention also provide the application of the above-mentioned hydrogen-bonded framework nanotrap materials in carbon trapping.
[0020] As a more preferred approach, CO2 is adsorbed in a mixed gas.
[0021] The beneficial effects of the embodiments of the present invention are:
[0022] This invention provides a method for preparing the hydrogen-bonded framework nanotrap material HOF-Cu-DAP-SO4, and directly applying the prepared HOF-Cu-DAP-SO4 material for efficient CO2 capture. This material is based on a unique chemical synthesis method, utilizing the interactions between metal salts, organic ligands, and inorganic anions to form a stable one-dimensional porous structure. This structure possesses a rich and well-ordered pore system with a high specific surface area, providing numerous accessible active sites and rapid diffusion channels for carbon dioxide molecules. Furthermore, its preparation method is simple, requiring only stirring at room temperature, without complex equipment or harsh conditions, making it easy to operate and control, and conducive to large-scale production.
[0023] This material exhibits excellent carbon capture capabilities. The HOF-Cu-DAP-SO4 has an adsorption capacity of up to 65.2 cm⁻¹ for CO₂. 3 g -1 It outperforms many traditional carbon capture materials. Its unique "nano-trap" structure gives it extremely high selectivity for CO2, enabling it to preferentially adsorb carbon dioxide in mixed systems containing nitrogen, methane, and other gases, providing a new and effective strategy for the efficient capture and separation of CO2. Attached Figure Description
[0024] Figure 1 This is a scanning electron microscope image of the hydrogen-bonded framework nanotrap material HOF-Cu-DAP-SO4 prepared in the embodiments of the present invention. Detailed Implementation
[0025] The technical solutions of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative effort are within the scope of protection of the present invention.
[0026] To address the shortcomings of existing carbon capture materials in terms of structure, performance, and preparation, this invention proposes a hydrogen-bonded framework nanotrap material, HOF-Cu-DAP-SO4, along with its preparation method and applications. This invention utilizes specific chemical synthesis methods and the interactions between metal salts, organic ligands, and inorganic anions to successfully prepare a hydrogen-bonded framework nanotrap material. This material possesses a unique one-dimensional channel structure, where precisely arranged Lewis basic amino groups within the channels synergistically form "nanotraps" with uncoordinated oxygen atoms in the inorganic sulfate columns, constructing functionalized molecular transport channels. This structure not only provides numerous adsorption active sites for carbon dioxide but also constructs pathways for rapid carbon dioxide transport, reducing transport resistance and significantly improving carbon dioxide adsorption efficiency. The preparation method of this hydrogen-bonded framework nanotrap material is simple, highly practical, and exhibits excellent performance in the field of carbon capture.
[0027] All reagents used in the following examples are commercially available.
[0028] The present invention provides a method for preparing a hydrogen-bonded framework nanotrap material, comprising the following steps:
[0029] 1) Dissolve CuSO4·5H2O in deionized water to form solution A, wherein the ratio of CuSO4·5H2O to deionized water is 80-100 mg: 2-2.5 mL;
[0030] 2) Add 2,6-diaminopurine to a mixed solvent consisting of N,N-dimethylacetamide (DMA) and deionized water to form solution B, wherein the amounts of 2,6-diaminopurine, N,N-dimethylacetamide and deionized water are 43.6-54.5 mg: 10-12 mL: 3-3.6 mL.
[0031] 3) Add solution A dropwise to solution B while continuously stirring to carry out the reaction. The dropping rate is 1-2 drops per second, the stirring reaction time is 48-72 hours, and the reaction temperature is room temperature.
[0032] 4) After the stirring reaction is complete, centrifugation is performed to obtain a precipitate, which is a grayish-blue precipitate. The precipitate is washed, and the washed product is vacuum dried to obtain the hydrogen-bonded framework nanotrap material HOF-Cu-DAP-SO4. The vacuum drying is performed at 333 K for 12-24 hours. The precipitate is washed sequentially with N,N-dimethylformamide (DMF), deionized water, and methanol, and centrifugation is performed after each wash.
[0033] The above-mentioned method for preparing hydrogen-bonded framework nanotrap materials is simple, requiring only stirring at room temperature, without the need for complex equipment or harsh conditions, and is easy to operate and control, which is conducive to large-scale production.
[0034] This invention also provides a hydrogen-bonded framework nanotrap material, HOF-Cu-DAP-SO4, prepared using the above-described method. This material, based on a unique chemical synthesis method, utilizes the interactions between metal salts, organic ligands, and inorganic anions to form a stable one-dimensional channel structure. Within the one-dimensional channels, precisely arranged Lewis basic amino groups and uncoordinated oxygen atoms in the inorganic sulfate columns synergistically form carbon dioxide "nanotraps," constructing transport channels with high affinity for carbon dioxide. This structure possesses a rich and well-ordered pore system with a high specific surface area, providing numerous accessible active sites and rapid diffusion channels for carbon dioxide molecules.
[0035] This invention also provides applications of the aforementioned hydrogen-bonded framework nanotrap material in carbon capture. Preferably, it is used for CO2 adsorption in mixed gases. This material exhibits superior carbon capture capabilities compared to many traditional carbon capture materials. Its unique "nanotrap" structure gives it extremely high selectivity for CO2, enabling preferential adsorption of carbon dioxide in mixed systems containing nitrogen, methane, and other gases. The material demonstrates excellent carbon dioxide adsorption performance and high selectivity for both nitrogen and methane. This invention, through precise pore engineering strategies to construct highly efficient molecular traps, provides a promising method for designing advanced adsorbents for efficient carbon capture, with broad application prospects in areas such as industrial waste gas carbon dioxide capture and biogas purification.
[0036] Example 1
[0037] Dissolve 80 mg (0.32 mmol) of CuSO4·5H2O in 2 mL of deionized water to form solution A.
[0038] 43.6 mg (0.29 mmol) of 2,6-diaminopurine was added to a mixed solvent consisting of 10 mL of DMA and 3 mL of deionized water to form solution B.
[0039] At room temperature, add solution A dropwise to solution B at a rate of 1-2 drops per second. After the addition is complete, continue stirring the mixture for 48 hours.
[0040] After the reaction was completed, the resulting gray-blue precipitate was collected by centrifugation. The precipitate was then washed three times each with DMF, deionized water, and methanol, and centrifuged after each wash. The washed product was dried under vacuum at 333 K for 12 h to obtain the hydrogen-bonded framework nanotrap material HOF-Cu-DAP-SO4.
[0041] Example 2
[0042] Dissolve 80 mg (0.32 mmol) of CuSO4·5H2O in 2 mL of deionized water to form solution A.
[0043] 43.6 mg (0.29 mmol) of 2,6-diaminopurine was added to a mixed solvent consisting of 10 mL of DMA and 3 mL of deionized water to form solution B.
[0044] At room temperature, add solution A dropwise to solution B at a rate of 1-2 drops per second. After the addition is complete, continue stirring the mixture for 72 hours.
[0045] After the reaction was completed, the resulting gray-blue precipitate was collected by centrifugation. The precipitate was then washed three times each with DMF, deionized water, and methanol, and centrifuged after each wash. The washed product was dried under vacuum at 333 K for 12 h to obtain the hydrogen-bonded framework nanotrap material HOF-Cu-DAP-SO4.
[0046] Example 3
[0047] Dissolve 100 mg (0.4 mmol) of CuSO4·5H2O in 2.5 mL of deionized water to form solution A.
[0048] 54.5 mg (0.36 mmol) of 2,6-diaminopurine was added to a mixed solvent consisting of 12 mL of DMA and 3.6 mL of deionized water to form solution B.
[0049] At room temperature, add solution A dropwise to solution B at a rate of 1-2 drops per second. After the addition is complete, continue stirring the mixture for 48 hours.
[0050] After the reaction was completed, the resulting gray-blue precipitate was collected by centrifugation. The precipitate was then washed three times each with DMF, deionized water, and methanol, and centrifuged after each wash. The washed product was dried under vacuum at 333 K for 12 h to obtain the hydrogen-bonded framework nanotrap material HOF-Cu-DAP-SO4.
[0051] Example 4
[0052] The only difference between Example 4 and Example 1 is that the cleaned product was dried in a vacuum environment of 333K for 18 hours.
[0053] Example 5
[0054] The only difference between Example 5 and Example 1 is that the cleaned product was dried in a vacuum environment of 333K for 24 hours.
[0055] Comparative Example
[0056] Commercially available ordinary activated carbon was selected as the comparative material.
[0057] Experimental Example 1
[0058] The hydrogen-bonded framework nanotrap material HOF-Cu-DAP-SO4 prepared in Example 1 was subjected to scanning electron microscopy (SEM), and the obtained SEM images are shown below. Figure 1 As shown. From Figure 1 It can be seen that the material forms a stable one-dimensional pore structure. This structure has a rich and regular pore system with a high specific surface area, providing a large number of accessible active sites and fast diffusion channels for carbon dioxide molecules.
[0059] Experiment Example 2
[0060] Carbon dioxide adsorption tests were conducted on the hydrogen-bonded framework nanotrap materials HOF-Cu-DAP-SO4 prepared in Examples 1-3, as well as the comparative materials provided in the comparative examples. The adsorption capacity of the materials for carbon dioxide was tested under the conditions of 298 K and 1 bar.
[0061] After testing, the CO2 adsorption capacity of the hydrogen-bonded framework nanotrap material HOF-Cu-DAP-SO4 prepared in Example 1 was found to be 61.9 cm⁻¹. 3 g -1 .
[0062] The hydrogen-bonded framework nanotrap material HOF-Cu-DAP-SO4 prepared in Example 2 has a CO2 adsorption capacity of 63.5 cm⁻¹. 3 g -1 .
[0063] The hydrogen-bonded framework nanotrap material HOF-Cu-DAP-SO4 prepared in Example 3 has a CO2 adsorption capacity of 65.2 cm⁻¹. 3 g -1 .
[0064] The comparative adsorbent material has a CO2 adsorption capacity of 20 cm⁻¹. 3 g -1 .
[0065] Therefore, it can be seen that the hydrogen-bonded framework nanotrap material HOF-Cu-DAP-SO4 prepared in the embodiments of the present invention has a much higher adsorption capacity for carbon dioxide than activated carbon, demonstrating the advantages of HOF-Cu-DAP-SO4 in carbon dioxide adsorption.
[0066] This invention provides a method for preparing the hydrogen-bonded framework nanotrap material HOF-Cu-DAP-SO4, and directly uses the prepared HOF-Cu-DAP-SO4 material for efficient CO2 capture. Compared with existing technologies, this invention has significant advantages. This material is based on a unique chemical synthesis method, utilizing the interactions between metal salts, organic ligands, and inorganic anions to form a stable one-dimensional porous structure. This structure possesses a rich and well-ordered porous system with a high specific surface area, providing numerous accessible active sites and rapid diffusion channels for carbon dioxide molecules. Furthermore, its preparation method is simple, requiring only stirring at room temperature, without complex equipment or harsh conditions, making it easy to operate and control, and conducive to large-scale production.
[0067] This material exhibits excellent carbon capture capabilities. The HOF-Cu-DAP-SO4 has an adsorption capacity of up to 65.2 cm⁻¹ for CO₂. 3 g -1 This material outperforms many traditional carbon capture materials. Its unique "nanotrap" structure gives it extremely high selectivity for CO2, enabling it to preferentially adsorb carbon dioxide in mixed systems containing nitrogen, methane, and other gases. This provides a new and effective strategy for the efficient capture and separation of CO2.
[0068] Based on the above-described preferred embodiments of the present invention, and through the foregoing description, those skilled in the art can make various changes and modifications without departing from the inventive concept. The technical scope of this invention is not limited to the contents of the specification.
Claims
1. A method for preparing a hydrogen-bonded framework nanotrap material, characterized in that, Includes the following steps: 1) Dissolve CuSO4·5H2O in deionized water to form solution A; 2) Add 2,6-diaminopurine to a mixed solvent consisting of N,N-dimethylacetamide and deionized water to form solution B; 3) Add solution A dropwise to solution B while continuously stirring to allow the reaction to proceed; 4) After the stirring reaction is completed, centrifugation is performed to obtain the precipitate. The precipitate is washed, and the washed product is dried under vacuum to obtain the hydrogen-bonded framework nanotrap material HOF-Cu-DAP-SO4.
2. The method for preparing the hydrogen-bonded framework nanotrap material according to claim 1, characterized in that, In step 1), the ratio of CuSO4·5H2O to deionized water is 80-100 mg: 2-2.5 mL.
3. The method for preparing the hydrogen-bonded framework nanotrap material according to claim 1, characterized in that, In step 2), the ratio of 2,6-diaminopurine, N,N-dimethylacetamide and deionized water is 43.6-54.5 mg: 10-12 mL: 3-3.6 mL.
4. The method for preparing the hydrogen-bonded framework nanotrap material according to claim 1, characterized in that, In step 3), the dropping rate is 1-2 drops per second, the stirring reaction time is 48-72 hours, and the reaction temperature is room temperature.
5. The method for preparing the hydrogen-bonded framework nanotrap material according to claim 1, characterized in that, In step 4), the vacuum drying is performed at a temperature of 333K for 12-24 hours.
6. The method for preparing the hydrogen-bonded framework nanotrap material according to any one of claims 1-5, characterized in that, In step 4), the precipitate is washed sequentially with N,N-dimethylformamide, deionized water, and methanol.
7. The method for preparing the hydrogen-bonded framework nanotrap material according to claim 6, characterized in that, In step 4), centrifugation is performed after each wash.
8. A hydrogen-bonded framework nanotrap material, characterized in that, It is prepared by the method for preparing hydrogen-bonded framework nanotrap materials according to any one of claims 1-7.
9. The application of the hydrogen-bonded framework nanotrap material as described in claim 8 in carbon trapping.
10. The application according to claim 9, characterized in that, Application of CO2 adsorption in mixed gases.