JP2020041112A - Covalent organic structure, covalent organic structure composition and method for producing covalent organic structure composition - Google Patents
Covalent organic structure, covalent organic structure composition and method for producing covalent organic structure composition Download PDFInfo
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本発明は、外的作用により変色するスイッチング現象を有する共有結合性有機構造体および共有結合性有機構造体組成物と、共有結合性有機構造体組成物の製造方法とに関するものである。 The present invention relates to a covalent organic structure and a covalent organic structure composition having a switching phenomenon that changes color by an external action, and a method for producing the covalent organic structure composition.
従来より、規則正しい細孔を形成することができる多孔質材料として、ホウ素含有化合物とアルコール類またはアルデヒド類の縮合物を熱処理して得られる共有結合性有機構造体が提案されている（特許文献１参照）。 Conventionally, as a porous material capable of forming regular pores, a covalent organic structure obtained by heat-treating a condensate of a boron-containing compound and an alcohol or aldehyde has been proposed (Patent Document 1). reference).
このような多孔質材料は、規則正しく、かつ、大きい比表面積を利用して、燃料貯蔵材料、温室効果ガスの分離・貯蔵材料、水質浄化材料として期待されている。しかし、上記従来のホウ素を含有した共有結合性有機構造体の場合、熱処理によって酸化ホウ素を生じることが懸念され、このような酸化ホウ素は、多孔質材料の空隙を閉じてしまうこととなり、熱処理前後で比表面積が大きく変化してしまうこととなり、良好な多孔質材料が得られない。 Such a porous material is expected as a fuel storage material, a greenhouse gas separation / storage material, and a water purification material by using a regular and large specific surface area. However, in the case of the conventional boron-containing covalent organic structure described above, there is a concern that boron oxide may be generated by the heat treatment, and such boron oxide will close the voids of the porous material, and before and after the heat treatment. As a result, the specific surface area changes greatly, and a good porous material cannot be obtained.
また、上記従来の共有結合性有機構造体は、空隙に水分を吸着させた場合、加水分解されてしまうことがあり、その後に水分を脱着させたり、再度、水分を吸着させたりして反復利用することができなくなることが懸念される。また、加熱、光照射などの外的作用を加えたりしても、当該共有結合性有機構造体自体が色変化するようなことはなく、これらの外的作用を認識することはできなかった。 In addition, the above-mentioned conventional covalent organic structure may be hydrolyzed when moisture is adsorbed in the voids, and then desorb the water or adsorb the water again to repeatedly use the organic structure. There is a concern that you will not be able to do so. In addition, even when an external action such as heating or light irradiation was applied, the covalent organic structure itself did not change color, and these external actions could not be recognized.
本発明は、係る実情に鑑みてなされたものであって、外的作用により変色するスイッチング現象を起こすことができる共有結合性有機構造体、共有結合性有機構造体組成物およびその製造方法を提供することを目的としている。 The present invention has been made in view of the above circumstances, and provides a covalent organic structure, a covalent organic structure composition, and a method of manufacturing the same, which are capable of causing a switching phenomenon that changes color by an external action. It is intended to be.
上記課題を解決するための本発明に係る共有結合性有機構造体は、下記式（Ａ）からなるものである。 A covalent organic structure according to the present invention for solving the above-mentioned problems is represented by the following formula (A).
上記共有結合性有機構造体は、下記式（Ｂ）からなるものであってもよい。 The above-mentioned covalent organic structure may have the following formula (B).
上記共有結合性有機構造体は、下記式(Ｃ）からなるものであってもよい。 The covalent organic structure may be represented by the following formula (C).
上記課題を解決するための本発明に係る共有結合性有機構造体組成物は、式（Ａ）の共有結合性有機構造体と、式（Ｂ）の共有結合性有機構造体と、式(Ｃ)の共有結合性有機構造体とからなる共有結合性有機構造体組成物であって、光や熱の作用により平衡状態が変化するものである。 In order to solve the above-mentioned problems, a covalent organic structure composition according to the present invention includes a covalent organic structure of the formula (A), a covalent organic structure of the formula (B), and a compound of the formula (C) ), Wherein the equilibrium state is changed by the action of light or heat.
上記共有結合性有機構造体組成物は、式（Ａ）の共有結合性有機構造体および式（Ｂ）の共有結合性有機構造体からなる共有結合性有機構造体組成物と、式（Ｃ）の共有結合性有機構造体および式（Ｂ）の共有結合性有機構造体からなる共有結合性有機構造体組成物との間において、水分の有無により平衡状態が変化するものであってもよい。 The above-mentioned covalent organic structure composition comprises a covalent organic structure composition comprising a covalent organic structure of the formula (A) and a covalent organic structure of the formula (B); The equilibrium state may be changed depending on the presence or absence of water between the covalent organic structure of formula (1) and the covalent organic structure composition comprising the covalent organic structure of formula (B).
上記共有結合性有機構造体組成物は、平衡状態が変化して変色するもであってもよい。 The covalent organic structure composition may change its equilibrium state and change color.
上記課題を解決するための本発明に係る共有結合性有機構造体組成物の製造方法は、下記２ヒドロキシ１，３，５−ベンゼントリカルボキシアルデヒド（以下、ＨＢＴＡという）と、１，４−ジアミノベンゼン（以下、ＤＡＢという）とを、１，４−ジオキサンの溶媒に加えた後、加熱反応させることによって得られるものである。 In order to solve the above-mentioned problems, a method for producing a covalent organic structure composition according to the present invention comprises the following 2-hydroxy-1,3,5-benzenetricarboxaldehyde (hereinafter, referred to as HBTA) and 1,4-diamino. It is obtained by adding benzene (hereinafter, referred to as DAB) to a solvent of 1,4-dioxane and subjecting it to a heating reaction.
上記式（Ａ）、式（Ｂ）、式（Ｃ）に示す共有結合性有機構造体は、それぞれ異性体であって、図１に示すように、３種類が混合された共有結合性有機構造体組成物の形で製造することができる。 The covalent organic structures represented by the above formulas (A), (B) and (C) are isomers, respectively, and as shown in FIG. It can be manufactured in the form of a body composition.
このうち、式（Ａ）に示すエノールフォームの共有結合性有機構造体は、式（Ｂ）に示すシスケトフォームの共有結合性有機構造体から吸熱する、または、式（Ｃ）に示すトランスケトフォームの共有結合性有機構造体を加熱することによって得ることができる。式（Ｂ）に示すシスケトフォームの共有結合性有機構造体は、式（Ａ）に示すエノールフォームの共有結合性有機構造体を加熱する、または、式（Ｃ）に示すトランスケトフォームの共有結合性有機構造体が発光することによって得ることができる。式（Ｃ）に示すトランスケトフォームの共有結合性有機構造体は、式（Ａ）に示す共有結合性有機構造体が吸光する、または、式（Ｂ）に示すシスケトフォームの共有結合性有機構造体が吸光することによって得ることができる。 Among these, the covalent organic structure of the enol foam represented by the formula (A) absorbs heat from the covalent organic structure of the cisketoform represented by the formula (B), or the transketoform represented by the formula (C) Can be obtained by heating the covalent organic structure. The covalent organic structure of the cisketo form represented by the formula (B) is obtained by heating the covalent organic structure of the enol form represented by the formula (A) or the covalent bond of the transketo form represented by the formula (C). It can be obtained by emitting light from the conductive organic structure. The covalent organic structure of the transketoform represented by the formula (C) is obtained by absorption of the covalent organic structure represented by the formula (A) or the covalent organic structure of the cisketoform represented by the formula (B) It can be obtained by light absorption by the body.
このように、上記した３種類の異性体を構成する共有結合性有機構造体は、加熱、吸熱、発光、吸光といった熱および／または光の作用により変化可能な平衡状態を保って混合された共有結合性有機構造体組成物を構成している。 As described above, the covalent organic structures constituting the above three types of isomers are mixed while maintaining an equilibrium state that can be changed by the action of heat and / or light, such as heating, endothermic, luminescent, and light absorption. It constitutes the binding organic structure composition.
また、上記式（Ａ）、式（Ｂ）、式（Ｃ）に示す共有結合性有機構造体は、それぞれ異性体であって、図２に示すように、式（Ａ）に示すエノールフォームの共有結合性有機構造体および式（Ｂ）に示すシスケトフォームの共有結合性有機構造体からなる共有結合性有機構造体組成物と、式（Ｃ）に示すトランスケトフォームの共有結合性有機構造体および式（Ｂ）に示すシスケトフォームの共有結合性有機構造体からなる共有結合性有機構造体組成物との間で、水分の有無により平衡状態が変化する共有結合性有機構造体組成物の形で製造することができる。 Further, the covalent organic structures shown in the above formulas (A), (B) and (C) are isomers, respectively, and as shown in FIG. A covalent organic structure composition comprising a covalent organic structure and a cisketoform covalent organic structure of formula (B), and a transketoform covalent organic structure of formula (C) And the form of the covalent organic structure composition whose equilibrium changes depending on the presence or absence of moisture between the covalent organic structure composition and the covalent organic structure composition of the cisketo foam represented by the formula (B). Can be manufactured.
この際、図３（ａ）に示すように、水分が無い場合は、式（Ａ）に示すエノールフォームの共有結合性有機構造体および式（Ｂ）に示すシスケトフォームの共有結合性有機構造体からなる共有結合性有機構造体組成物を構成し、赤褐色の色を呈する。また、図３（ｂ）に示すように、水分を吸収した場合は、式（Ｃ）に示すトランスケトフォームの共有結合性有機構造体および式（Ｂ）に示すシスケトフォームの共有結合性有機構造体からなる共有結合性有機構造体組成物を構成し、黒色の色を呈する。 At this time, as shown in FIG. 3 (a), when there is no moisture, the covalent organic structure of the enol foam represented by the formula (A) and the covalent organic structure of the cisketo foam represented by the formula (B) And forms a reddish brown color. Further, as shown in FIG. 3 (b), when moisture is absorbed, the covalent organic structure of the transketoform represented by the formula (C) and the covalent organic structure of the cisketoform represented by the formula (B) are obtained. It constitutes a covalent organic structure composition consisting of a body and exhibits a black color.
このように、平衡状態の変化に伴って色の変化を生じるスイッチング現象を起こすので、上記した共有結合性有機構造体組成物は、高い比表面積を利用した材料としてだけでなく、このスイッチング現象を利用した各種材料として利用できる。したがって、例えば、可視可能なガス吸着センサ（水分吸着状態は黒、水分放出状態は赤褐色の粉末）を構成したり、樹脂に練り混ぜてガスバリア性の樹脂材料を構成したり、特定サイズのガスは吸着・透過させるが、ある特定以上の大きさのガスは通さない選択的ガス吸着を行うガス篩を構成したり、湿度によって変色する湿度計を構成したり、水分吸着剤（乾燥剤）として構成したりすることができる。また、水を加えると黒変し、アセトンを加えると赤褐色に変色するので、どの溶媒を吸着したのかを判断する（選択的溶媒分子の貯蓄を行う）材料として利用したりすることができる。さらに、シス型とトランス型との間の変化で細孔のサイズが大きくなったり小さくなったり変化するので、この異性体の変化による細孔のサイズ変化のスイッチング現象を利用して特定のガスをトラップしたり放出させたりする材料として利用したりすることができる。すなわち、細孔が大きい状態で特定のガスをトラップし、その後、細孔を小さく変化させてその構造を維持することで、特定のガスをトラップすることができる。また、細孔が大きい状態で特定のガスを吸着させた後、細孔を小さく変化させた状態を維持すると、細孔が小さくなり、吸着したガスがかなりの時間をかけないと細孔外に放出されなくなるので、これを利用してトラップした特定のガスの放出速度を制御する材料として利用したりすることができる。 As described above, since a switching phenomenon that causes a color change in accordance with a change in the equilibrium state occurs, the above-described covalent organic structure composition is not only a material using a high specific surface area, but also this switching phenomenon. It can be used as various materials used. Therefore, for example, a visible gas adsorption sensor (water adsorption state is black, water release state is red-brown powder), or a resin material having gas barrier properties by mixing with resin, Constructs a gas sieve that performs selective gas adsorption that adsorbs and permeates but does not allow gas of a certain size or larger to pass, configures a hygrometer that changes color depending on humidity, or configures as a moisture adsorbent (drying agent) Or you can. Further, when water is added, the color changes to black, and when acetone is added, the color changes to reddish brown, so that it can be used as a material for judging which solvent is adsorbed (selective storage of solvent molecules). Further, since the pore size changes depending on the change between the cis-form and the trans-form, the specific gas is utilized by utilizing the switching phenomenon of the pore size change due to the change of the isomer. It can be used as a trapping or releasing material. That is, a specific gas can be trapped by trapping a specific gas in a state where the pores are large, and then changing the pores to a small size and maintaining the structure. In addition, after a specific gas is adsorbed in a state where the pores are large, if the state in which the pores are changed to a small value is maintained, the pores become small, and the adsorbed gas cannot be taken out of the pores without taking a considerable time. Since it is no longer released, it can be used as a material for controlling the release rate of the trapped specific gas by using this.
上記共有結合性有機構造体組成物の製造方法において、合成工程での反応条件としては、上記したＨＢＴＡとＤＡＢとを、１，４−ジオキサンの溶媒に加えた後、加熱反応させることによって、共有結合を有する有機構造体組成物を構成することができるものであれば、特に限定されるものではなく、必要に応じて加熱、加圧、減圧、攪拌、冷却等の操作が行われる。これらは、複数の操作を組み合わせる場合も、段階的に行う場合も含む。共有結合性有機構造体組成物としては、格子状、六角形状等の規則性のある環状の構造体が連なった形状のものを形成するものであれば、特に限定されるものではなく、有機多孔体（ＣＯＦ：Covalent Organic Framework)の一般的な形状を形成するものは含まれる。例えば、５０〜２５０℃程度の温度で、３〜１００時間程度の反応を行うことによって形成される。温度は段階的に昇温および／または冷却する場合も含む。また、圧力は、段階的に加圧および／または減圧する場合も含む。 In the method for producing the covalent organic structure composition, the reaction conditions in the synthesis step are as follows. The HBTA and DAB are added to a solvent of 1,4-dioxane, and then heated to cause a reaction. The material is not particularly limited as long as it can constitute the organic structure composition having a bond, and operations such as heating, pressurizing, depressurizing, stirring, and cooling are performed as necessary. These include a case where a plurality of operations are combined and a case where the operations are performed stepwise. The covalent organic structure composition is not particularly limited as long as it forms a shape in which a cyclic structure having regularity such as a lattice or a hexagon is formed. Those that form the general shape of the body (COF: Covalent Organic Framework) are included. For example, it is formed by performing a reaction at a temperature of about 50 to 250 ° C. for about 3 to 100 hours. The temperature includes a case where the temperature is raised and / or cooled stepwise. The pressure also includes a case where the pressure is increased and / or reduced stepwise.
ただし、上記した各共有結合性有機構造体の異性体は、反応条件等によってバランスが異なるため、反応条件は適宜調整される。 However, the isomers of the above-described covalent organic structures have different balances depending on the reaction conditions and the like, so that the reaction conditions are appropriately adjusted.
本発明に係る共有結合性有機構造体組成物は、焼成して共有結合性有機構造体組成物焼成体（以下、単に焼成体という。）にしてから利用するものであってもよい。 The covalent organic structure composition according to the present invention may be used after firing to form a covalent organic structure composition fired body (hereinafter simply referred to as a fired body).
以上述べたように、本発明の共有結合性有機構造体によると、水分の存在の有無により平衡状態が変化して変色する共有結合性有機構造体組成物を構成したり、熱および／または光の作用により平衡状態が変化して変色する共有結合性有機構造体組成物を構成したりするので、比表面積が大きい多孔質材料としてのみならず、これらのスイッチング現象を利用した各種製品の原料として利用できる。 As described above, according to the covalent organic structure of the present invention, a covalent organic structure composition that changes its equilibrium state and changes its color depending on the presence or absence of moisture, or has heat and / or light Or the composition of the covalent organic structure, which changes color by changing the equilibrium state, not only as a porous material with a large specific surface area, but also as a raw material for various products utilizing these switching phenomena. Available.
以下、本発明に係る実施の形態について説明する。 Hereinafter, embodiments of the present invention will be described.
［実施例１］
（粉末（合成材料））
下記式（１）で表される分子構造の２ヒドロキシ１，３，５−ベンゼントリカルボキシアルデヒド（以下、ＨＢＴＡという）と、下記式（２）で表される分子構造の１，４−ジアミノベンゼン（以下、ＤＡＢという）の２種類の粉末を使用した。
[Example 1]
(Powder (synthetic material))
2-hydroxy-1,3,5-benzenetricarboxaldehyde (hereinafter referred to as HBTA) having a molecular structure represented by the following formula (1) and 1,4-diaminobenzene having a molecular structure represented by the following formula (2) (Hereinafter referred to as DAB).
（触媒）
１，４−ジオキサンを溶媒として使用した。
(catalyst)
1,4-dioxane was used as a solvent.
（共有結合性有機構造体組成物の合成）
ＨＢＴＡ：０．０４８ｇ、ＤＡＢ：０．０４８ｇ、１，４−ジオキサン：３ｍＬを、５０ｍＬ用水熱合成容器（ＨＵ−５０：三愛科学株式会社製）内に入れたものを６セット作製した。その後、それら６セットの５０ｍＬ用水熱合成容器（以下、水熱合成容器という）を３０分間超音波分散させた後、１２０℃で７２時間加熱して共有結合性有機構造体組成物の合成（脱水縮合による合成）を行った。合成後、上澄みを捨てて、新たに低水分アセトン８００ミリリットルを加えて、１０分程度５０℃で加熱攪拌し、７日間放置した。７日後、上澄み液を回収し、粉末を１２０℃で２０時間減圧下で乾燥させた。
このようにして得られた共有結合性有機構造体組成物は、赤褐色であった。
(Synthesis of Covalent Organic Structure Composition)
Six sets were prepared by placing 0.048 g of HBTA, 0.048 g of DAB, and 3 mL of 1,4-dioxane in a 50 mL hydrothermal synthesis vessel (HU-50: manufactured by San-ai Science Co., Ltd.). Thereafter, the six sets of 50 mL hydrothermal synthesis vessels (hereinafter referred to as hydrothermal synthesis vessels) are ultrasonically dispersed for 30 minutes, and then heated at 120 ° C. for 72 hours to synthesize (dehydrate) the covalent organic structure composition. Synthesis by condensation). After the synthesis, the supernatant was discarded, 800 ml of low-moisture acetone was newly added, and the mixture was heated and stirred at 50 ° C. for about 10 minutes and left for 7 days. After 7 days, the supernatant was collected and the powder was dried under reduced pressure at 120 ° C. for 20 hours.
The covalent organic structure composition thus obtained was reddish brown.
（電子顕微鏡写真）
上記で得られた共有結合性有機構造体組成物の電子顕微鏡写真を撮影した。
撮影条件は下記の通りである。結果を図４に示す。
測定機種：JSM-6010LA（日本電子株式会社製）
測定条件：加速電圧１５ｋＶ、ワーキングディスタンス１１ｍｍ、スポットサイズ３０、測定倍率：１０００倍、５０００倍、１００００倍
その結果、真球に近い複数の球体の集合体のような共有結合性有機構造体組成物が得られていることが確認できた。
(Electron micrograph)
An electron micrograph of the covalent organic structure composition obtained above was taken.
The photographing conditions are as follows. FIG. 4 shows the results.
Measurement model: JSM-6010LA (manufactured by JEOL Ltd.)
Measurement conditions: acceleration voltage 15 kV, working distance 11 mm, spot size 30, measurement magnification: 1000 ×, 5000 ×, 10000 × As a result, a covalent organic structure composition such as an aggregate of a plurality of spheres close to a true sphere Was confirmed to have been obtained.
（粉末Ｘ線回折）
上記で得られた共有結合性有機構造体組成物を赤褐色の状態および黒色の状態で、それぞれの粉末約０．０２ｇを、サンプルホルダーに乗せて整地し、回折を行った。測定機種、測定条件などは下記の通りである。結果を図５に示す。
測定機種：Ｘ線回折装置RINT-Ultima+（株式会社リガク製）
測定条件：測定角度の範囲は２θ＝２°〜４０°
スキャンスピード４°／ｍｉｎ
(Powder X-ray diffraction)
About 0.02 g of each powder of the covalent organic structure composition obtained above was placed in a sample holder in a reddish-brown state and a black state, and diffraction was performed. The measurement models and measurement conditions are as follows. FIG. 5 shows the results.
Measurement model: X-ray diffractometer RINT-Ultima + (manufactured by Rigaku Corporation)
Measurement conditions: The range of the measurement angle is 2θ = 2 ° to 40 °
Scan speed 4 ° / min
（窒素吸着測定（比表面積/細孔分布測定））
上記で得られた共有結合性有機構造体組成物を２００℃で５時間減圧乾燥させ、室温雰囲気中で当該共有結合性有機構造体組成物に吸着した水分を脱着させて赤褐色にした後、当該共有結合性有機構造体組成物の粉末０．０２ｇをサンプル管に入れ、液体窒素雰囲気下で比表面積/細孔分布測定装置（BELLSORP-miniII：マイクロトラックベル株式会社）
によって窒素吸着等温曲線を測定した。また、同装置の解析プログラム（I型（ISO9277
）ＢＥＴ自動解析）により比表面積を算出した。結果を図６に示す。
(Nitrogen adsorption measurement (specific surface area / pore distribution measurement))
The covalent organic structure composition obtained above is dried under reduced pressure at 200 ° C. for 5 hours, and the water adsorbed on the covalent organic structure composition is desorbed in a room temperature atmosphere to turn red-brown. 0.02 g of the powder of the covalent organic structure composition is placed in a sample tube, and the specific surface area / pore distribution measuring device (BELLSORP-miniII: Microtrack Bell Co., Ltd.) is placed in a liquid nitrogen atmosphere.
The nitrogen adsorption isotherm was measured by the method. In addition, the analysis program (type I (ISO9277
) BET automatic analysis) to calculate the specific surface area. FIG. 6 shows the results.
（水分の有無による考察）
このようにして得られた共有結合性有機構造体組成物を入れたガラスビンの蓋を開けたまま、室温環境の雰囲気下に放置しておいたところ、空気中の水分を吸湿して約１０分程で黒色に変化した。
この黒色に変化した共有結合性有機構造体組成物が入ったガラスビンをヒーターにかけて９０℃で加熱したところ、共有結合性有機構造体組成物は、元の赤褐色に戻り、加熱過程では、加熱によって放出された水分がガラスビンの上部に付着していた。この経過を図７に示す。
(Consideration based on the presence or absence of water)
The glass bottle containing the thus obtained covalent organic structure composition was left open in an atmosphere of a room temperature environment with the lid open, and it absorbed moisture in the air for about 10 minutes. The color changed to black.
When the glass bottle containing the covalent organic structure composition that turned black was heated at 90 ° C. with a heater, the covalent organic structure composition returned to the original reddish brown color and was released by heating in the heating process. The drained water adhered to the upper part of the glass bottle. This process is shown in FIG.
以上の結果から、本発明に係る共有結合性有機構造体組成物は、水分の有無により平衡状態が変化して可逆的に色が変化することが確認できた。また、９９０ｍ2／ｇの高い比表面積が得られていることが確認できた。 From the above results, it was confirmed that the covalent organic structure composition according to the present invention changed the equilibrium state depending on the presence or absence of moisture and changed color reversibly. It was also confirmed that a high specific surface area of 990 m 2 / g was obtained.
なお、本発明は、その精神または主要な特徴から逸脱することなく、他のいろいろな形で実施することができる。そのため、上述の実施例はあらゆる点で単なる例示に過ぎず、限定的に解釈してはならない。本発明の範囲は特許請求の範囲によって示すものであって、明細書本文には、なんら拘束されない。さらに、特許請求の範囲に属する変形や変更は、全て本発明の範囲内のものである。 Note that the present invention can be embodied in various other forms without departing from the spirit or main characteristics thereof. Therefore, the above-described embodiment is merely an example in all aspects, and should not be construed as limiting. The scope of the present invention is defined by the claims, and is not limited by the text of the specification. Further, all modifications and changes belonging to the claims are within the scope of the present invention.
Claims (7)
２ヒドロキシ１，３，５−ベンゼントリカルボキシアルデヒドと、１，４−ジアミノベンゼンとを、１，４−ジオキサンの溶媒に加えた後、加熱反応させることによって得られる共有結合性有機構造体組成物の製造方法。 It is a manufacturing method of the covalent organic structure composition of Claim 5, Comprising:
Covalently bonding organic structure composition obtained by adding 2-hydroxy 1,3,5-benzenetricarboxaldehyde and 1,4-diaminobenzene to a solvent of 1,4-dioxane and then subjecting the mixture to a heating reaction. Manufacturing method.
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| CN114106276A (en) * | 2021-12-07 | 2022-03-01 | 中国科学院兰州化学物理研究所 | Preparation method of shape-controllable covalent organic framework material |
| CN116178646A (en) * | 2022-12-11 | 2023-05-30 | 三峡大学 | Preparation method of high-entropy covalent organic framework compound |
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