An acylhydrazone-linked covalent organic framework material, its preparation method and application
Patent Information
- Application Number
- CN202510200774.7
- Authority / Receiving Office
- CN · China
- Patent Type
- Patents(China)
- Current Assignee / Owner
- Filing Date
- 2025-02-24
- Publication Date
- 2026-01-06
- Estimated Expiration
- 2045-02-24
AI Technical Summary
[0003]虽然目前已经有多种合成酰腙连接的COFs材料的方法，但仍存在一些问题，如制备的酰腙连接的共价有机框架材料的结晶性和稳定性低等
[0026]1、本发明以苯并[1,2-b:3,4-b':5,6-b”]三噻吩-2,5,8-三甲醛和特定结构的苯二酰肼为主要原料，通过调整催化剂的浓度、种类以及用量制备得到了具有更高结晶性和稳定性的酰腙连接的共价有机框架材料。
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Figure CN119978275B_ABST
Abstract
Description
Technical Field
[0001] This invention belongs to the field of covalent organic framework material synthesis technology, and more specifically relates to an acylhydrazone-linked covalent organic framework material, its preparation method and application. Background Technology
[0002] With the continuous development of materials science, the demand for novel materials with specific properties and structures is increasing. Traditional inorganic porous materials and organic-inorganic hybrid materials have limitations in some aspects, such as high density, poor structural designability, and complex synthesis processes. In 2005, Yaghi's research group first reported the synthesis of covalent organic framework materials (COFs) with crystalline structures through the dehydration condensation reaction of boric acid, opening a new era in COF material research.
[0003] Although various methods exist for synthesizing acylhydrazone-linked covalent organic frameworks (COFs), some problems remain, such as low crystallinity and stability of the prepared COFs. Therefore, further exploration and development of synthetic methods for acylhydrazone-linked COFs with higher crystallinity and stability are needed to achieve large-scale preparation and application. Summary of the Invention
[0004] The purpose of this invention is to provide an acylhydrazone-linked covalent organic framework material, its preparation method, and its application, so as to solve the problems existing in the prior art and realize the preparation and application of acylhydrazone-linked covalent organic framework materials with higher crystallinity and stability.
[0005] To achieve the above objectives, the present invention provides the following solution:
[0006] One of the technical solutions of this invention is to provide an acylhydrazone-linked covalent organic framework material, wherein the structural unit of the acylhydrazone-linked covalent organic framework material is:
[0007] Where “﹉” indicates an omitted structural repeating unit, and R is selected from -OCH2CH3 or -OCH2CHCH2.
[0008] The second technical solution of the present invention provides a method for preparing the acylhydrazone-linked covalent organic framework material, comprising the following steps:
[0009] Benzo[1,2-b:3,4-b':5,6-b”]trithiophene-2,5,8-tricarboxaldehyde, benzodiazepine, o-dichlorobenzene (o-DCB) and n-butanol were mixed to obtain suspension A;
[0010] Trifluoroacetic acid (TFA) was added to the suspension A and mixed to obtain mixture A;
[0011] The mixture A was subjected to freeze degassing and heating treatment in sequence, and then extracted to obtain the acylhydrazone-linked covalent organic framework material.
[0012] This invention uses benzo[1,2-b:3,4-b':5,6-b”]trithiophene-2,5,8-tricarboxaldehyde and benzodiazepines with a specific structure as main raw materials. By adjusting the concentration and amount of trifluoroacetic acid, a covalent organic framework material with higher crystallinity and stability was prepared. Because the covalent organic framework material prepared by this invention contains acylhydrazone bonds, it ensures higher crystallinity and stability. Higher crystallinity and stability guarantee that the covalent organic framework material with acylhydrazone linkage exhibits excellent adsorption, separation, and stability.
[0013] Preferably, the ratio of benzo[1,2-b:3,4-b':5,6-b”]trithiophene-2,5,8-tricarboxaldehyde, benzodiazepine, and o-dichlorobenzene is 0.075–0.085 mmol:0.11–0.14 mmol:1.5 mL.
[0014] Preferably, the volume ratio of o-dichlorobenzene to n-butanol is 1:1.
[0015] By adjusting the volume ratio of o-dichlorobenzene to n-butanol, appropriate solubility of the reactants can be ensured. Solubility above the upper limit of this range will lead to a decrease in crystallinity, while solubility below the lower limit of this range will lead to a decrease in the degree of polymerization.
[0016] Preferably, the trifluoroacetic acid is added in the form of an aqueous trifluoroacetic acid solution; the concentration of the aqueous trifluoroacetic acid solution is 3-4 M; and the volume ratio of the aqueous trifluoroacetic acid solution to o-dichlorobenzene is 30-40 μL:1.5 mL.
[0017] The solubility and reactivity of the reaction products can be improved by adjusting the concentration and amount of trifluoroacetic acid catalyst. Exceeding the upper limit of this range will lead to the destruction of crystallinity, while falling below the lower limit of this range will lead to a decrease in the degree of polymerization.
[0018] Preferably, the structural formula of the phenylhydrazine is:
[0019] Wherein, R is selected from -OCH2CH3 or -OCH2CHCH2.
[0020] By selecting benzo[1,2-b:3,4-b':5,6-b”]trithiophene-2,5,8-tricarboxaldehyde and benzo[1,2-b:3,4-b':5,6-b”]trithiophene-2,5,8-tricarboxaldehyde with a specific structure, the stability of the framework structure can be improved through the electronic interaction of the branched chain, thereby preparing a covalent organic framework material with higher crystallinity and stability.
[0021] Preferably, the number of times the freeze-degassing is performed is 2 to 5.
[0022] Preferably, the heat treatment is performed at a temperature of 120–180°C for 3–5 days.
[0023] Preferably, the reagents used for extraction include tetrahydrofuran and N,N-dimethylformamide; the extraction time is 48–72 h.
[0024] The third technical solution of this invention provides the application of the aforementioned acylhydrazone-linked covalent organic framework material in the field of electrochemical energy storage.
[0025] The present invention discloses the following technical effects:
[0026] 1. This invention uses benzo[1,2-b:3,4-b':5,6-b”]trithiophene-2,5,8-tricarboxaldehyde and benzodiazepines with a specific structure as the main raw materials. By adjusting the concentration, type and amount of the catalyst, a covalent organic framework material with higher crystallinity and stability is prepared.
[0027] 2. This invention has low requirements for synthesis, simple preparation process, and uses readily available raw materials, thus having better application prospects. Attached Figure Description
[0028] Figure 1 This is a schematic diagram illustrating the synthesis of the acylhydrazone-linked covalent organic framework material described in this invention;
[0029] Figure 2 This is a schematic diagram illustrating the synthesis of the acylhydrazone-linked covalent organic framework material described in Example 1;
[0030] Figure 3 This is a schematic diagram illustrating the synthesis of the acylhydrazone-linked covalent organic framework material described in Example 2;
[0031] Figure 4 This is a schematic diagram illustrating the synthesis of the acylhydrazone-linked covalent organic framework material described in Example 3;
[0032] Figure 5 The XRD pattern without characteristic peaks is shown for the acylhydrazone-linked covalent organic framework material numbered 1 in Example 1.
[0033] Figure 6 The weak characteristic peak XRD pattern of the acylhydrazone-linked covalent organic framework material No. 3 described in Example 1;
[0034] Figure 7 The XRD pattern of the acylhydrazone-linked covalent organic framework material (number 9) described in Example 1 shows the strong characteristic peak shape.
[0035] Figure 8 The XRD pattern without characteristic peaks is shown for the acylhydrazone-linked covalent organic framework material numbered 1 in Example 2.
[0036] Figure 9 The weak characteristic peak XRD pattern of the acylhydrazone-linked covalent organic framework material numbered 3 in Example 2;
[0037] Figure 10 The XRD pattern of the strong characteristic peak shape of the acylhydrazone-linked covalent organic framework material (number 9) described in Example 2;
[0038] Figure 11 The XRD pattern without characteristic peaks is shown for the acylhydrazone-linked covalent organic framework material numbered 6 in Example 3.
[0039] Figure 12 The XRD pattern for the stability test of the acylhydrazone-linked covalent organic framework material numbered 6 in Example 1;
[0040] Figure 13 The XRD pattern is for the stability test of the acylhydrazone-linked covalent organic framework material No. 6 described in Example 2. Detailed Implementation
[0041] Various exemplary embodiments of the present invention will now be described in detail. This detailed description should not be considered as a limitation of the present invention, but rather as a more detailed description of certain aspects, features, and embodiments of the present invention.
[0042] It should be understood that the terminology used in this invention is merely for describing particular embodiments and is not intended to limit the invention. Furthermore, with respect to numerical ranges in this invention, it should be understood that each intermediate value between the upper and lower limits of the range is also specifically disclosed. Any stated value or intermediate value within a stated range, as well as each smaller range between any other stated value or intermediate value within said range, is also included in this invention. The upper and lower limits of these smaller ranges may be independently included or excluded from the range.
[0043] Unless otherwise stated, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art. While only preferred methods and materials have been described herein, any methods and materials similar or equivalent to those described herein may be used in the implementation or testing of this invention. All references to this specification are incorporated by way of citation to disclose and describe methods and / or materials associated with those references. In the event of any conflict with any incorporated reference, the content of this specification shall prevail.
[0044] 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 readily apparent to those skilled in the art. This specification and embodiments are merely exemplary.
[0045] 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.
[0046] The raw materials used in the embodiments of the present invention are described below:
[0047] The benzo[1,2-b:3,4-b':5,6-b”]trithiophene-2,5,8-tricarboxaldehyde used was purchased from Bid Pharmaceuticals.
[0048] The 2,5-diethoxybenzene-1,4-dicarboxyhydrazide used was synthesized in the laboratory.
[0049] The 1,4-dicarboxyhydrazide used was purchased from Adamas.
[0050] The 2,5-bis(allyloxy) terephthalohydrazide used was purchased from Bidex Pharmaceuticals.
[0051] The o-dichlorobenzene (o-DCB) used was purchased from Adamas.
[0052] The n-butanol used was purchased from Adamas.
[0053] The trifluoroacetic acid (TFA) used was purchased from Adamas.
[0054] The acetic acid (AcOH) used was purchased from Adamas.
[0055] Unless otherwise specified, all other raw materials are commercially available products.
[0056] This invention provides an acylhydrazone-linked covalent organic framework material with higher crystallinity and stability, and the specific synthesis process is as follows: Figure 1 As shown, this invention solves the problem of poor self-healing covalent bond formation in existing technologies due to the difficulty in crystallizing covalent organic framework materials. Obtaining covalent organic framework materials with high crystallinity and stable pore structure still presents many challenges, and this invention also addresses the issue of low stability in existing covalent organic framework materials, which hinders their later applications.
[0057] Example 1
[0058] This embodiment verifies the preparation of acylhydrazone-linked covalent organic framework materials under different catalyst types, amounts, concentrations, and heating reaction times when R in phenylhydrazone is selected from -OCH2CH3. The details are as follows:
[0059] Preparation steps:
[0060] Benzo[1,2-b:3,4-b':5,6-b”]trithiophene-2,5,8-tricarboxaldehyde (26.4 mg) and benzodiazepine (R selected from -OCH2CH3) (33.8 mg) were dissolved in o-dichlorobenzene (o-DCB) (1.5 mL), and then n-butanol (1.5 mL) was added to obtain a suspension; then a catalyst (including acetic acid (AcOH) or trifluoroacetic acid (TFA), both added in aqueous solution) was added to the suspension, and the mixture was shaken for 5 min; the sample was then subjected to... The sample was degassed three times by freezing; heated at 120°C; after the reaction was completed, the sample was cooled to room temperature, the precipitate was filtered, and washed three times with acetone (10 mL) and tetrahydrofuran (10 mL) until the eluent was clear. The solid obtained was subjected to Soxhlet extraction for 72 h in a mixed solvent of tetrahydrofuran and N,N-dimethylformamide (volume ratio of tetrahydrofuran and N,N-dimethylformamide was 1:1). The solid was then vacuum dried to obtain a yellow powder, which is the acylhydrazone-linked covalent organic framework material, denoted as BTT-TH-COF.
[0061] The catalyst type, dosage, concentration, and heating reaction time corresponding to this embodiment are shown in Table 1.
[0062] Table 1
[0063]
[0064] Nine products were prepared according to the above preparation method and the parameters in Table 1.
[0065] Figure 2 This is a schematic diagram illustrating the synthesis of the acylhydrazone-linked covalent organic framework material described in Example 1.
[0066] Figure 5 The XRD pattern without characteristic peaks is shown for the acylhydrazone-linked covalent organic framework material numbered 1 in Example 1. Figure 6 The weak characteristic peak XRD pattern of the acylhydrazone-linked covalent organic framework material No. 3 described in Example 1; Figure 7 The image shows the strong characteristic peak shape XRD pattern of the acylhydrazone-linked covalent organic framework material (number 9) described in Example 1.
[0067] Example 2
[0068] This embodiment verifies the preparation of acylhydrazone-linked covalent organic framework materials under different catalyst types, amounts, concentrations, and heating reaction times when R in phenylhydrazone is selected from -OCH2CHCH2. The details are as follows:
[0069] Preparation steps:
[0070] Benzo[1,2-b:3,4-b':5,6-b”]trithiophene-2,5,8-tricarboxaldehyde (26.4 mg) and benzodiazepine (R selected from -OCH2CHCH2) (33.8 mg) were dissolved in o-dichlorobenzene (o-DCB) (1.5 mL), and then n-butanol (1.5 mL) was added to obtain a suspension; then a catalyst (including acetic acid (AcOH) or trifluoroacetic acid (TFA), both added in aqueous solution) was added to the suspension and shaken for 5 min; the sample was then injected... The sample was degassed three times by freezing; heated at 120°C; after the reaction was completed, the sample was cooled to room temperature, the precipitate was filtered, and washed three times with acetone (10 mL) and tetrahydrofuran (10 mL) until the eluent was clear. The solid obtained was extracted by Soxhlet extraction for 72 h in a mixed solvent of tetrahydrofuran and N,N-dimethylformamide (volume ratio of tetrahydrofuran and N,N-dimethylformamide was 1:1). The solid was dried under vacuum to obtain a yellow powder, which is the acylhydrazone-linked covalent organic framework material, denoted as BTT-TH-COF.
[0071] The catalyst type, dosage, concentration, and heating reaction time corresponding to this embodiment are shown in Table 2.
[0072] Table 2
[0073]
[0074]
[0075] Nine products were prepared according to the above preparation method and the parameters in Table 1.
[0076] Figure 3 This is a schematic diagram illustrating the synthesis of the acylhydrazone-linked covalent organic framework material described in Example 2.
[0077] Figure 8 The XRD pattern without characteristic peaks is shown for the acylhydrazone-linked covalent organic framework material numbered 1 in Example 2. Figure 9 The weak characteristic peak XRD pattern of the acylhydrazone-linked covalent organic framework material numbered 3 in Example 2; Figure 10 The XRD pattern of the strong characteristic peak shape of the acylhydrazone-linked covalent organic framework material (number 9) described in Example 2;
[0078] Example 3
[0079] This embodiment verifies the preparation of acylhydrazone-linked covalent organic framework materials under different catalyst types, amounts, concentrations, and heating reaction times when R in phenylhydrazone is selected as -H. The details are as follows:
[0080] Preparation steps:
[0081] Benzo[1,2-b:3,4-b':5,6-b”]trithiophene-2,5,8-tricarboxaldehyde (26.4 mg) and benzo[R](-H)-selected benzo[H](-H)-methylbenzene(2,4-b':5,6-b”)-2,5,8-tricarboxaldehyde (33.8 mg) were dissolved in o-dichlorobenzene (o-DCB) (1.5 mL), and then n-butanol (1.5 mL) was added to obtain a suspension. A catalyst (including acetic acid (AcOH) or trifluoroacetic acid (TFA), both added in aqueous solution) was then added to the suspension, and the mixture was shaken for 5 min. The sample was then subjected to freeze-drying. The gas was heated three times; the reaction was carried out at 120℃; after the reaction was completed, the sample was cooled to room temperature, the precipitate was filtered, and the precipitate was washed three times with acetone (10 mL) and tetrahydrofuran (10 mL) until the eluent was clear. The solid obtained was subjected to Soxhlet extraction for 72 h in a mixed solvent of tetrahydrofuran and N,N-dimethylformamide (the volume ratio of tetrahydrofuran and N,N-dimethylformamide was 1:1). The solid was then vacuum dried to obtain a yellow powder, which is the acylhydrazone-linked covalent organic framework material, denoted as BTT-TH-COF.
[0082] The catalyst type, dosage, concentration, and heating reaction time corresponding to this embodiment are shown in Table 3.
[0083] Table 3
[0084]
[0085] Nine products were prepared according to the above preparation method and the parameters in Table 1.
[0086] Figure 4 This is a schematic diagram illustrating the synthesis of the acylhydrazone-linked covalent organic framework material described in Example 3.
[0087] Figure 11 The XRD pattern without characteristic peaks is shown for the acylhydrazone-linked covalent organic framework material numbered 6 in Example 3.
[0088] Performance verification:
[0089] The crystallinity and stability of the 27 products obtained in Examples 1-3 were verified:
[0090] Crystallinity: The crystallinity of the obtained product is related to the intensity of the small-angle diffraction peak in XRD. As shown in Tables 1 to 3, when R in benzodiazepine is selected as -H, the obtained product has no crystallinity. However, the product prepared by this invention has excellent crystallinity.
[0091] Stability: The stability of product number 6 obtained in Example 1 and product number 6 obtained in Example 2 under different reagents was determined, and the results are as follows: Figure 12 and Figure 13 As shown.
[0092] Figure 12The XRD pattern for the stability test of the acylhydrazone-linked covalent organic framework material numbered 6 in Example 1; Figure 13 This is the XRD pattern for the stability test of the acylhydrazone-linked covalent organic framework material (number 6) described in Example 2. Figures 12-13 It can be seen that the acylhydrazone-linked covalent organic framework material No. 6 described in Example 1 and the acylhydrazone-linked covalent organic framework material No. 6 described in Example 2 both have excellent stability. Since the acylhydrazone-linked covalent organic framework materials synthesized in Example 3 are not crystallizable, their stability will not be discussed.
[0093] The various embodiments in this specification are described in a progressive manner, with each embodiment focusing on the differences from other embodiments. The same or similar parts between the various embodiments can be referred to each other.
[0094] The above description of the disclosed embodiments enables those skilled in the art to make or use the invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the general principles defined herein may be implemented in other embodiments without departing from the spirit or scope of the invention. Therefore, the invention is not to be limited to the embodiments shown herein, but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims
1. A method for preparing an acylhydrazone-linked covalent organic framework material with high crystallinity and stability, characterized in that, The structural unit of the acylhydrazone-linked covalent organic framework material is: wherein "— " indicates an omitted structural repeat unit, R is selected from -OCH2CHCH2; The preparation steps of the acylhydrazone-linked covalent organic framework material are as follows: benzo[1,2-b:3,4-b':5,6-b'']trithiophene-2,5,8-tricarboxaldehyde, benzene dihydrazide, o-dichlorobenzene and n-butanol are mixed to obtain a suspension A; trifluoroacetic acid is added to the suspension A to obtain a mixture A; the mixture A is sequentially subjected to freeze-drying and heating treatment, and then extracted to obtain the acylhydrazone-linked covalent organic framework material; the amount ratio of the benzo[1,2-b:3,4-b':5,6-b'']trithiophene-2,5,8-tricarboxaldehyde, benzene dihydrazide and o-dichlorobenzene is 0.075~0.085 mmol:0.11~0.14 mmol:1.5 mL; the volume ratio of the o-dichlorobenzene and n-butanol is 1:1; the trifluoroacetic acid is added in the form of a trifluoroacetic acid aqueous solution; the concentration of the trifluoroacetic acid aqueous solution is 3M; the volume ratio of the trifluoroacetic acid aqueous solution and o-dichlorobenzene is 30~40 μL:1.5 mL; the structural formula of the benzene dihydrazide is: wherein R is selected from -OCH2CHCH2; the temperature of the heating treatment is 120℃, and the time is 3d.
2. The production method according to claim 1, characterized by, the number of freeze-drying is 2~5 times.
3. The preparation method according to claim 1, characterized in that, the reagents used for the extraction include tetrahydrofuran and N,N-dimethylformamide; the time of the extraction is 48~72h.