TW201522084A - Two-dimensional graphene-based porous polymer and the preparation thereof - Google Patents
Two-dimensional graphene-based porous polymer and the preparation thereof Download PDFInfo
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- TW201522084A TW201522084A TW103125929A TW103125929A TW201522084A TW 201522084 A TW201522084 A TW 201522084A TW 103125929 A TW103125929 A TW 103125929A TW 103125929 A TW103125929 A TW 103125929A TW 201522084 A TW201522084 A TW 201522084A
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Classifications
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/48—Conductive polymers
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/32—Carbon-based
- H01G11/36—Nanostructures, e.g. nanofibres, nanotubes or fullerenes
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/32—Carbon-based
- H01G11/38—Carbon pastes or blends; Binders or additives therein
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/13—Energy storage using capacitors
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Abstract
Description
本發明係關於一種多孔聚合物。特定言之，本發明係關於一種夾心型二維石墨基多孔聚合物，且更特定言之，本發明係關於一種夾心型二維石墨基微孔聚合物、其產生方法及其用途。 This invention relates to a porous polymer. In particular, the present invention relates to a sandwich type two-dimensional graphite-based porous polymer, and more particularly, to a sandwich type two-dimensional graphite-based microporous polymer, a method for producing the same, and uses thereof.
具有奈米尺度之孔隙率之多孔聚合物已由於其與突出物理特性及潛在應用，諸如光捕獲、感測、氣體分離及儲存、催化及能量儲存及轉化相關聯之多孔特徵而引起巨大關注。存在若干類別之微孔/中孔聚合物，諸如超級交聯聚合物(HCP)、內在微孔聚合物(PIM)及共價有機框架(COF)。亦可根據多孔聚合物之結構構形將其分類為非結晶型(諸如HCP及PIM)或結晶型(諸如COF)材料。共軛微孔聚合物(CPP)代表多孔材料中發展最快的類型中之一者，不僅由於其對於習知金屬催化聚合技術之高效率及大量市售官能單體之可用性，且亦由於其可控及可調物理特性。不同於COF，CPP係在動力學控制下形成，且因此為非晶的且不顯示長程結構有序。出於此原因，關於CPP之大部分先前工作集中於開發新穎化學策略及藉由改變有機連接子長度而非經由形態控制調整此等聚合物之孔徑分佈及表面積。最近，已致力於合成具有控制奈米結構之CPP，諸如準零維(quasi-zero-dimensional)微球，及一維奈米纖維及奈米管以及三 維單塊。然而，合成具有二維(2D)薄片結構之多孔聚合物仍未進行深入探索。Colson等人採用溶劑熱法藉由硼酸及六羥基聯伸三苯單體之動態組合在基板負載之石墨烯上生長定向二維COF薄膜，但尚未大規模生產獨立式二維多孔聚合物網狀物。 Porous polymers having nanometer-scale porosity have received significant attention due to their porous characteristics associated with outstanding physical properties and potential applications such as light capture, sensing, gas separation and storage, catalysis, and energy storage and conversion. There are several classes of microporous/mesoporous polymers such as super crosslinked polymers (HCP), intrinsic microporous polymers (PIM), and covalent organic frameworks (COF). The porous polymer may also be classified into an amorphous type (such as HCP and PIM) or a crystalline type (such as COF) material according to the structural configuration of the porous polymer. Conjugated microporous polymers (CPP) represent one of the fastest growing types of porous materials, not only because of their high efficiency for conventional metal catalyzed polymerization techniques and the availability of a large number of commercially available functional monomers, but also because of their Controllable and adjustable physical characteristics. Unlike COF, CPP is formed under kinetic control and is therefore amorphous and does not exhibit long-range structural order. For this reason, much of the prior work on CPP has focused on developing novel chemical strategies and adjusting the pore size distribution and surface area of such polymers by changing the length of the organic linker rather than via morphological control. Recently, efforts have been made to synthesize CPPs with controlled nanostructures, such as quasi-zero-dimensional microspheres, and one-dimensional nanofibers and nanotubes, and three Dimensions. However, the synthesis of porous polymers having a two-dimensional (2D) sheet structure has not yet been explored in depth. Colson et al. used a solvothermal method to grow a directional two-dimensional COF film on substrate-supported graphene by dynamic combination of boric acid and hexa-hydroxy-terminated triphenyl monomer, but has not yet mass-produced a free-standing two-dimensional porous polymer network. .
在最近十年中開發諸如共軛微孔聚合物[Jiang等人Conjugated microporous poly(arylene ethynylene)networks.Angew.Chem.Int.Edit.2007,46(45),8574-8578.]、基於希夫鹼(Schiff base)之多孔聚合物[Schwab等人Catalyst-free Preparation of Melamine-Based Microporous Polymer Networks through Schiff Base Chemistry.J.Am.Chem.Soc.2009,131(21),7216-7217]及多種其他類型之多孔聚合物的多孔聚合物。然而，關於形態控制報導之著作極稀少。 Developed in the last decade, such as conjugated microporous polymers [Jiang et al. Conjugated microporous poly (arylene ethynylene networks networks. Angew. Chem. Int. Edit. 2007, 46 (45), 8574-8857.], based on Schiff Schiff base porous polymer [Schwab et al. Catalyst-free Preparation of Melamine-Based Microporous Polymer Networks through Schiff Base Chemistry. J. Am. Chem. Soc. 2009, 131 (21), 7216-7217] and various Porous polymers of other types of porous polymers. However, the work on morphological control reports is extremely rare.
Colson等人已成功開發一種用於產生基於基板負載之石墨烯模板的二維COF之溶劑熱縮合方法[Colson Oriented 2D Covalent Organic Framework Thin Films on Single-Layer Graphene.Science 2011,332(6026),228-231]。在此溶劑熱縮合方法中，將基板負載之單層石墨烯浸沒至含有1,4-伸苯基雙(硼酸)(PBBA)及2,3,6,7,10,11-六羥基聯伸三苯(HHTP)之均三甲苯：二噁烷(1：1 v/v)溶液中，且接著將混合物保持於溶劑熱條件下。COF-5(基於1,4-伸苯基雙(硼酸)及2,3,6,7,10,11-六羥基聯伸三苯之共價有機框架)可以於底部之不溶粉末形式產生且亦可以石墨烯表面上之連續膜形式產生。然而，此報導方法受到反應瓶之石墨烯面積及體積的限制且無法容易地按比例增加。大部分單體縮合為COF-5且自溶液沈澱，而非負載於石墨烯表面上。石墨烯與COF-5之間的相互作用極弱。另外，合成之 COF基材料之穩定性極弱。COF-5僅負載於石墨烯之一側上。 Colson et al. have successfully developed a solvothermal condensation process for the production of two-dimensional COF based on substrate-loaded graphene templates [Colson Oriented 2D Covalent Organic Framework Thin Films on Single-Layer Graphene. Science 2011, 332 (6026), 228 -231]. In the solvothermal condensation method, the substrate-supported single layer graphene is immersed to contain 1,4-phenylene bis(borate) (PBBA) and 2,3,6,7,10,11-hexahydroxyl extension Benzene (HHTP) in a solution of mesitylene: dioxane (1:1 v/v), and then the mixture is maintained under solvothermal conditions. COF-5 (a covalent organic framework based on 1,4-phenylene bis(borate) and 2,3,6,7,10,11-hexahydroxy-terminated triphenyl) can be produced in the form of an insoluble powder at the bottom and also It can be produced as a continuous film on the surface of graphene. However, this reporting method is limited by the graphene area and volume of the reaction flask and cannot be easily scaled up. Most of the monomers condense into COF-5 and precipitate from the solution rather than being supported on the graphene surface. The interaction between graphene and COF-5 is extremely weak. In addition, synthetic The stability of COF-based materials is extremely weak. COF-5 is only supported on one side of the graphene.
在先前著作[Yang等人Graphene-Based Nanosheets with a Sandwich Structure.Angew.Chemie Int.Edition 2010,49(28),4795-4799]中，藉由使用石墨基中孔二氧化矽薄片作為模板及使用蔗糖作為碳源在高溫下熱解，接著移除二氧化矽模板製備二維多孔碳。前述方法首次提供一種用於製備二維多孔碳之新穎方法，然而，使用無機中孔二氧化矽模板為極關鍵的。難以精細調整之孔資訊，諸如孔直徑、孔深度及孔體積來自石墨烯表面上之多孔二氧化矽之孔。以此方法，將有惡臭的二氧化矽薄片用作硬模板以將碳源填充至其孔中，接著進行高溫熱解且接著使用高毒性及危險性HF溶液蝕刻二氧化矽模板。隨後對獲得之樣品進行真空乾燥以產生最終二維多孔碳。此多步合成方法需要就人力、時間及金錢而言之較高資本成本。此外，碳源為極有限的。 In the previous work [Yang et al. Graphene-Based Nanosheets with a Sandwich Structure. Angew . Chemie Int . Edition 2010, 49 (28), 4795-4799], by using graphite-based mesoporous cerium oxide sheets as templates and using Sucrose is pyrolyzed as a carbon source at a high temperature, and then the ceria template is removed to prepare a two-dimensional porous carbon. The foregoing method provides for the first time a novel method for preparing two-dimensional porous carbon, however, the use of an inorganic mesoporous ceria template is extremely critical. Hole information that is difficult to fine tune, such as pore diameter, pore depth, and pore volume, is derived from the pores of the porous ceria on the surface of the graphene. In this way, a malodorous ceria sheet is used as a hard template to fill the carbon source into its pores, followed by high temperature pyrolysis and then etching the ceria template using a highly toxic and hazardous HF solution. The obtained sample was then vacuum dried to produce a final two-dimensional porous carbon. This multi-step synthesis method requires a higher capital cost in terms of manpower, time and money. In addition, the carbon source is extremely limited.
因此，用以獲得多孔聚合物及/或多孔碳之所有上述途徑具有若干具挑戰性之態樣。因此，需要鑑別以大規模及具成本效益的方式產生穩定多孔聚合物及/或多孔碳之新穎「綠色」途徑。 Therefore, all of the above approaches for obtaining porous polymers and/or porous carbon have several challenging aspects. Therefore, there is a need to identify novel "green" pathways for producing stable porous polymers and/or porous carbons in a large scale and cost effective manner.
為移除先前技術中之缺陷，本發明提供一種新穎多孔聚合物及多孔碳，及其產生方法。 To remove the deficiencies of the prior art, the present invention provides a novel porous polymer and porous carbon, and a method of producing the same.
特定言之，本發明提供一種二維夾心型、石墨基微孔聚合物及自其獲得之多孔碳且提供用於產生其之方法。 In particular, the present invention provides a two-dimensional sandwich type, graphite-based microporous polymer and porous carbon obtained therefrom and providing a method for producing the same.
在本發明中，石墨烯層較佳藉由共價鍵包夾於多孔聚合物之間。在此提出之反應系統中，大部分單體聚合至石墨烯表面上。產生之 二維石墨基多孔聚合物極穩定且可容易以大規模合成。 In the present invention, the graphene layer is preferably sandwiched between the porous polymers by covalent bonding. In the reaction system proposed herein, most of the monomers are polymerized onto the surface of the graphene. Produced The two-dimensional graphite-based porous polymer is extremely stable and can be easily synthesized on a large scale.
在本發明中，可容易地以一鍋法產生二維石墨基多孔聚合物。可進一步僅藉由一步高溫熱解製備相關的二維石墨基多孔碳。此外，可分別藉由調節單體單元之長度及使用具有不同雜原子之單體在孔隙直徑及雜原子類型方面調整二維石墨基多孔聚合物之性質。 In the present invention, a two-dimensional graphite-based porous polymer can be easily produced in a one-pot process. The related two-dimensional graphite-based porous carbon can be further prepared by only one-step high-temperature pyrolysis. Further, the properties of the two-dimensional graphite-based porous polymer can be adjusted in terms of pore diameter and hetero atom type by adjusting the length of the monomer unit and using monomers having different hetero atoms, respectively.
圖1顯示製備石墨基二維共軛微孔聚合物(GMP)及自其產生之石墨基二維中孔碳(GMC)之流程(流程1)。 Figure 1 shows the flow of preparing a graphite-based two-dimensional conjugated microporous polymer (GMP) and graphite-based two-dimensional mesoporous carbon (GMC) produced therefrom (Scheme 1).
圖2顯示含硫共軛微孔聚合物(MP-S，非石墨基)及含硫石墨基二維共軛微孔聚合物(GMP-S)之微孔粒度分佈。 Figure 2 shows the pore size distribution of a sulfur-containing conjugated microporous polymer (MP-S, non-graphite based) and a sulfur-containing graphite-based two-dimensional conjugated microporous polymer (GMP-S).
圖3顯示合成希夫鹼型二維石墨基多孔聚合物之流程(流程2)。 Figure 3 shows the flow of synthesizing a Schiff base type two-dimensional graphite-based porous polymer (Scheme 2).
圖4顯示石墨基二維共軛微孔聚合物之SEM、TEM及AFM影像。 Figure 4 shows SEM, TEM and AFM images of a graphite-based two-dimensional conjugated microporous polymer.
圖5顯示在6M KOH溶液中於10mV s-1下的含硫中孔碳(MC-S，非石墨基)及含硫石墨基二維中孔碳(GMC-S)之CV曲線(左側)及在0.1Ag-1之電流密度下的MC-S及GMC-S之恆電流充電/放電曲線(右側)。 Figure 5 shows the CV curve of sulfur-containing mesoporous carbon (MC-S, non-graphite based) and sulfur-containing graphite-based two-dimensional mesoporous carbon (GMC-S) at 10 mV s -1 in 6 M KOH solution (left side) And the constant current charge/discharge curve (right side) of MC-S and GMC-S at a current density of 0.1 Ag -1 .
圖6顯示如在實施例6中解釋的二維中孔碳(PC-1，非石墨基)及二維石墨基多孔碳-1(TPC-1)聚合物之電化學效能資料，(a)在10mV s-1下於6M KOH中之循環伏安圖，(b)充電/放電曲線，(c)電化學阻抗譜及(d)用於電化學測試之電池裝置的示意圖。 Figure 6 shows electrochemical performance data of two-dimensional mesoporous carbon (PC-1, non-graphite based) and two-dimensional graphite-based porous carbon-1 (TPC-1) polymer as explained in Example 6, (a) Cyclic voltammogram in 6 M KOH at 10 mV s -1 , (b) charge/discharge curve, (c) electrochemical impedance spectroscopy and (d) schematic of a battery device for electrochemical testing.
圖7顯示在550-600nm下監測到的含硫共軛微孔聚合物(MP-S，非石墨基)及含硫石墨基二維共軛微孔聚合物(GMP-S)之螢光衰減及對應的 伸展指數擬合(λex=400nm)。 Figure 7 shows the fluorescence decay of sulfur-containing conjugated microporous polymers (MP-S, non-graphite based) and sulfur-containing graphite-based two-dimensional conjugated microporous polymers (GMP-S) monitored at 550-600 nm. And the corresponding stretch index fit (λ ex =400 nm).
除非另外規定，否則本文中所用之所有技術及科學術語具有與任一本發明所屬領域之一般熟習此項技術者通常所理解相同之含義。 Unless otherwise specified, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art.
表述「一(a/an)」、「該(the)」當用於定義術語時，包括術語之複數及單數形式二者。 The expression "a" or "the" when used to define a term includes both the plural and the singular.
在本發明中，術語「二維」意謂本發明之石墨基多孔聚合物之形態為具有大於2之縱橫比(長度或寬度比厚度)的薄片。 In the present invention, the term "two-dimensional" means that the form of the graphite-based porous polymer of the present invention is a sheet having an aspect ratio (length or width to thickness) of more than 2.
在本發明中，術語「石墨基二維多孔聚合物」、術語「二維、石墨基多孔聚合物」及術語「二維石墨基多孔聚合物」及其類似者可互換使用，其意謂多孔聚合物為二維的，且為石墨基的。「石墨基二維多孔碳」及術語「二維石墨基多孔碳」同樣如此。 In the present invention, the term "graphite-based two-dimensional porous polymer", the term "two-dimensional, graphite-based porous polymer" and the term "two-dimensional graphite-based porous polymer" and the like are used interchangeably, which means porous. The polymer is two-dimensional and graphite-based. The same applies to "graphite-based two-dimensional porous carbon" and the term "two-dimensional graphite-based porous carbon".
在本發明中，術語「微孔」意謂具有小於2nm之寬度的孔，術語「中孔」意謂具有2-50nm之間的寬度之孔，且術語「大孔」意謂具有大於50nm之寬度的孔。 In the present invention, the term "microporous" means a pore having a width of less than 2 nm, the term "mesopore" means a pore having a width of between 2 and 50 nm, and the term "macroporous" means having a diameter of more than 50 nm. Width of the hole.
在本發明之第一態樣中，本發明係關於一種石墨基二維多孔聚合物，其中石墨烯層包夾於多孔聚合物之間，石墨基二維多孔聚合物較佳為微孔的，且石墨烯層較佳藉由共價鍵包夾於多孔聚合物之間。 In a first aspect of the invention, the invention relates to a graphite-based two-dimensional porous polymer in which a graphene layer is sandwiched between porous polymers, and the graphite-based two-dimensional porous polymer is preferably microporous. And the graphene layer is preferably sandwiched between the porous polymers by a covalent bond.
不希望受任何理論束縛，咸信本發明之多孔聚合物呈網狀物形式，在多孔聚合物之間包夾有石墨烯層。多孔聚合物之孔由聚合物之單體單元之相互作用形成。藉由在聚合期間改變具有不同長度及/或不同雜原子之單體，可容易調節本發明之二維石墨基多孔聚合物之孔徑及本發明 之二維石墨基多孔聚合物中之雜原子。 Without wishing to be bound by any theory, it is believed that the porous polymer of the present invention is in the form of a network in which a graphene layer is sandwiched between porous polymers. The pores of the porous polymer are formed by the interaction of monomer units of the polymer. The pore size of the two-dimensional graphite-based porous polymer of the present invention can be easily adjusted by changing monomers having different lengths and/or different heteroatoms during polymerization and the present invention A hetero atom in a two-dimensional graphite-based porous polymer.
本發明之二維、石墨基多孔聚合物之聚合並非關鍵，其限制條件為聚合可用以製備本發明之多孔聚合物。舉例而言，可藉由溶液聚合製備本發明之二維、石墨基多孔聚合物。在本發明之一個較佳具體實例中，自縮合，諸如醛-胺基縮合獲得本發明之二維、石墨基多孔聚合物。在本發明之另一較佳具體實例中，藉由偶合反應方法，諸如薗頭偶合反應方法獲得本發明之二維、石墨基多孔聚合物。 The polymerization of the two-dimensional, graphite-based porous polymer of the present invention is not critical, and the limitation is that the polymerization can be used to prepare the porous polymer of the present invention. For example, the two-dimensional, graphite-based porous polymer of the present invention can be prepared by solution polymerization. In a preferred embodiment of the invention, the two-dimensional, graphite-based porous polymer of the present invention is obtained by self-condensation, such as aldehyde-amine condensation. In another preferred embodiment of the invention, the two-dimensional, graphite-based porous polymer of the present invention is obtained by a coupling reaction process, such as a taro coupling reaction process.
此外，可在任何適合於形成多孔聚合物之溫度及壓力下進行本發明之二維、石墨基多孔聚合物之聚合。在本發明之一些具體實例中，在0至200℃、較佳0至150℃或10至100℃之間的溫度及1-10標準大氣壓、較佳1-5標準大氣壓，諸如2-3標準大氣壓之間的壓力下進行本發明之聚合。 Furthermore, the polymerization of the two-dimensional, graphite-based porous polymer of the present invention can be carried out at any temperature and pressure suitable for forming a porous polymer. In some embodiments of the invention, the temperature is between 0 and 200 ° C, preferably between 0 and 150 ° C or between 10 and 100 ° C and between 1 and 10 standard atmospheres, preferably between 1 and 5 standard atmospheres, such as the 2-3 standard. The polymerization of the present invention is carried out under pressure between atmospheric pressure.
適合於形成本發明之二維、石墨基多孔聚合物之單體可為任何可由熟習此項技術者選擇的可聚合為多孔聚合物之單體。舉例而言，實際上所有含鹵素型單體、醛型單體及炔烴型單體適合於本發明。較佳地，含二鹵素型單體，更佳二溴型單體，諸如2,5-二溴噻吩、2,5-二溴-1,3-噻唑、2,6-二溴吡啶、3,8-二溴啡啉、5,5'-二溴-2,2'-聯吡啶、3,6-二溴嗒、6,6'-二溴靛藍、2,4-二溴噻唑、4,7-二溴-2,1,3-苯并噻二唑；二醛型單體，諸如1,3-苯二醛、1,4-苯二醛、2,5-噻吩二醛、4,4'-聯苯二醛及2,6-吡啶二醛；及三炔烴型單體，諸如1,3,5-三乙炔基苯、參(4-乙炔基苯基)胺為適合於本發明之單體。此外，含三鹵素型單體及含四鹵素型單體，較佳三溴型單體及四溴型單體，諸如2,4,6-三溴吡啶及5,10,15,20-肆-(4-溴苯基)-卟啉-M，其 中M=Zn、Cu、Co、Fe、Ni、Pt、Pd等為適合於本發明之單體。另外，含胺基型單體，例如三胺型單體，諸如三聚氰胺亦適合於本發明。在本發明之一些較佳具體實例中，三聚氰胺用於形成本發明之二維、石墨基多孔聚合物。在一些較佳具體實例中，在本發明中使用二醛/三胺或二溴/三乙炔型單體。 The monomer suitable for forming the two-dimensional, graphite-based porous polymer of the present invention can be any monomer which can be polymerized into a porous polymer, which can be selected by those skilled in the art. For example, virtually all halogen-containing monomers, aldehyde-type monomers, and alkyne-type monomers are suitable for the present invention. Preferably, it contains a dihalogen type monomer, more preferably a dibromo type monomer such as 2,5-dibromothiophene, 2,5-dibromo-1,3-thiazole, 2,6-dibromopyridine, 3 , 8-dibromomorpholine, 5,5'-dibromo-2,2'-bipyridine, 3,6-dibromoindole , 6,6'-dibromoindigo, 2,4-dibromothiazole, 4,7-dibromo-2,1,3-benzothiadiazole; dialdehyde type monomer, such as 1,3-benzene Aldehydes, 1,4-benzenedialdehyde, 2,5-thiophenedialdehyde, 4,4'-biphenyldialdehyde and 2,6-pyridinedialdehyde; and triacetylene type monomers such as 1,3,5 - Triethynylbenzene, ginseng (4-ethynylphenyl)amine is a monomer suitable for the present invention. Further, a trihalogen-type monomer and a tetrahalogen-containing monomer are preferred, and a tribromo-type monomer and a tetrabromo-type monomer such as 2,4,6-tribromopyridine and 5,10,15,20-fluorene are preferred. -(4-bromophenyl)-porphyrin-M, wherein M = Zn, Cu, Co, Fe, Ni, Pt, Pd, etc. are monomers suitable for the present invention. Further, an amine group-containing monomer such as a triamine type monomer such as melamine is also suitable for the present invention. In some preferred embodiments of the invention, melamine is used to form the two dimensional, graphite based porous polymer of the present invention. In some preferred embodiments, a dialdehyde/triamine or dibromo/triacetylenic monomer is used in the present invention.
在本發明之一個較佳具體實例中，本發明之二維、石墨基多孔聚合物為二維、石墨基共軛多孔聚合物或希夫鹼(Schiff-base)型二維、石墨基多孔聚合物。 In a preferred embodiment of the present invention, the two-dimensional, graphite-based porous polymer of the present invention is a two-dimensional, graphite-based conjugated porous polymer or Schiff-base type two-dimensional, graphite-based porous polymerization. Things.
以上列出之單體可用於形成本發明之二維、石墨基共軛多孔聚合物，諸如含鹵素型單體及炔烴型單體。在本發明之一些較佳具體實例中，用於形成本發明之二維、石墨基共軛多孔聚合物之單體係選自由以下各者組成之群：含二鹵素型單體，較佳二溴型單體，諸如2,5-二溴噻吩、2,5-二溴-1,3-噻唑、2,6-二溴吡啶、3,8-二溴啡啉、5,5'-二溴-2,2'-聯吡啶、3,6-二溴嗒、6,6'-二溴靛藍、2,4-二溴噻唑、4,7-二溴-2,1,3-苯并噻二唑；二醛型單體，諸如1,3-苯二醛、1,4-苯二醛、2,5-噻吩二醛、4,4'-聯苯二醛及2,6-吡啶二醛；及三炔烴型單體，諸如1,3,5-三乙炔基苯、參(4-乙炔基苯基)胺；及含三鹵素型單體及含四鹵素型單體，較佳三溴型單體，及四溴型單體，諸如2,4,6-三溴吡啶及5,10,15,20-肆-(4-溴苯基)-卟啉-M，其中M=Zn、Cu、Co、Fe、Ni、Pt、Pd等。 The monomers listed above can be used to form the two-dimensional, graphite-based conjugated porous polymers of the present invention, such as halogen-containing monomers and alkyne-type monomers. In some preferred embodiments of the invention, the single system used to form the two-dimensional, graphitic conjugated porous polymer of the present invention is selected from the group consisting of dihalogen containing monomers, preferably two Bromo type monomers such as 2,5-dibromothiophene, 2,5-dibromo-1,3-thiazole, 2,6-dibromopyridine, 3,8-dibromomorpholine, 5,5'-di Bromo-2,2'-bipyridine, 3,6-dibromofluorene , 6,6'-dibromoindigo, 2,4-dibromothiazole, 4,7-dibromo-2,1,3-benzothiadiazole; dialdehyde type monomer, such as 1,3-benzene Aldehydes, 1,4-benzenedialdehyde, 2,5-thiophenedialdehyde, 4,4'-biphenyldialdehyde and 2,6-pyridinedialdehyde; and triacetylene type monomers such as 1,3,5 a triethynylbenzene, a stilbene (4-ethynylphenyl)amine; and a trihalogen-containing monomer and a tetrahalogen-containing monomer, preferably a tribromo-type monomer, and a tetrabromo-type monomer such as 2, 4,6-tribromopyridine and 5,10,15,20-fluorene-(4-bromophenyl)-porphyrin-M, wherein M = Zn, Cu, Co, Fe, Ni, Pt, Pd and the like.
較佳地，可自不同類型之兩種或兩種以上單體之聚合獲得本發明之石墨基二維多孔聚合物。在一些具體實例中，兩種不同類型單體之混合物用於獲得本發明之石墨基二維多孔聚合物，諸如用於獲得本發明 之二維、石墨基共軛多孔聚合物或希夫鹼型二維、石墨基多孔聚合物。在一些較佳具體實例中，以AmBn形式混合單體，其中A及B分別表示如以上列出之單體類型，且m為單體A中之單體臂之數目，且n為單體B中之單體臂之數目，其中術語「單體臂」意謂參與聚合之單體之官能基，且其中m>n2或n>m2或n=m>2。 Preferably, the graphite-based two-dimensional porous polymer of the present invention can be obtained by polymerization of two or more monomers of different types. In some embodiments, a mixture of two different types of monomers is used to obtain the graphite-based two-dimensional porous polymer of the present invention, such as for obtaining a two-dimensional, graphite-based conjugated porous polymer or Schiff base type of the present invention. Two-dimensional, graphite-based porous polymer. In some preferred embodiments, the monomers are mixed in the form of A m B n , wherein A and B represent the monomer types as listed above, respectively, and m is the number of monomer arms in monomer A, and n is The number of monomer arms in monomer B, wherein the term "monomeric arms" means the functional groups of the monomers involved in the polymerization, and wherein m > n 2 or n>m 2 or n=m>2.
舉例而言，為製備本發明之希夫鹼型二維、石墨基多孔聚合物，根據AmBn之模式涉及兩種類型之單體，其包括醛型單體及含胺基型單體，諸如二醛型單體及三胺型單體，或三醛型單體及三胺型單體，或三醛型單體及二胺型單體，或三聚氰胺及二醛型單體或其類似物。 For example, to prepare the Schiff base type two-dimensional, graphite-based porous polymer of the present invention, the mode according to A m B n involves two types of monomers including an aldehyde type monomer and an amine group-containing monomer. , such as dialdehyde type monomers and triamine type monomers, or trialdehyde type monomers and triamine type monomers, or trialdehyde type monomers and diamine type monomers, or melamine and dialdehyde type monomers or analog.
在製備本發明之二維、石墨基共軛多孔聚合物之一些具體實例中，根據AmBn之模式僅使用鹵素型單體及炔烴型單體，諸如二溴型單體及三炔烴單體，或三溴型單體及二炔烴單體，或四溴型單體及二炔烴單體或其類似物。 In some specific examples of preparing the two-dimensional, graphite-based conjugated porous polymer of the present invention, only halogen type monomers and alkyne type monomers such as dibrominated type monomers and triacetylenes are used according to the mode of A m B n . a hydrocarbon monomer, or a tribromo-type monomer and a di-alkyne monomer, or a tetrabromo-type monomer and a di-alkyne monomer or the like.
在本發明之一些較佳具體實例中，用於形成本發明之二維、石墨基共軛多孔聚合物之單體含有含鹵素型單體，諸如二溴型單體、三溴型單體或四溴型單體及二炔烴型單體或三炔烴型單體二者，其根據以上提及之模式混合。 In some preferred embodiments of the invention, the monomer used to form the two-dimensional, graphitic conjugated porous polymer of the present invention contains a halogen-containing monomer such as a dibromo-type monomer, a tribromo-type monomer or Both tetrabromo-type monomers and di-alkyne type monomers or tri-alkyne type monomers are mixed according to the modes mentioned above.
在本發明之一些較佳具體實例中，用於形成本發明之希夫鹼型二維、石墨基多孔聚合物之單體可選自由以下各者組成之群：三聚氰胺及二醛單體，諸如1,3-苯二醛、1,4-苯二醛、2,5-噻吩二醛、4,4'-聯苯二醛及2,6-吡啶二醛。較佳地，用於形成本發明之希夫鹼型二維、石墨基多孔聚合物之單體包括三聚氰胺及二醛型單體，諸如1,3-苯二醛、1,4-苯二醛、 2,5-噻吩二醛、4,4'-聯苯二醛及2,6-吡啶二醛，其根據以上提及之模式混合。 In some preferred embodiments of the invention, the monomers used to form the Schiff base type two-dimensional, graphite-based porous polymer of the present invention may be selected from the group consisting of melamine and dialdehyde monomers, such as 1,3-benzenedialdehyde, 1,4-benzenedialdehyde, 2,5-thiophenedialdehyde, 4,4'-biphenyldialdehyde and 2,6-pyridinedialdehyde. Preferably, the monomer for forming the Schiff base type two-dimensional, graphite-based porous polymer of the present invention comprises a melamine and a dialdehyde type monomer such as 1,3-benzenedialdehyde or 1,4-benzenedialdehyde. , 2,5-thiophenedialdehyde, 4,4'-biphenyldialdehyde and 2,6-pyridinedialdehyde, which are mixed according to the modes mentioned above.
本發明之二維、石墨基多孔聚合物可藉由在結構中使用具有雜原子、金屬及金屬氧化物之單體或反應物將該等雜原子、金屬及金屬氧化物整合至聚合物之碳架中以用於各種應用，諸如能量儲存及電化學催化。藉由聚合，該等雜原子、金屬及金屬氧化物轉移至獲得之聚合物。在本發明中，在該情況下，將其稱作本發明之二維、石墨基多孔聚合物摻雜有雜原子、金屬或金屬氧化物。 The two-dimensional, graphite-based porous polymer of the present invention can integrate the heteroatoms, metals and metal oxides into the carbon of the polymer by using monomers or reactants having heteroatoms, metals and metal oxides in the structure. It is used in a variety of applications such as energy storage and electrochemical catalysis. The heteroatoms, metals and metal oxides are transferred to the obtained polymer by polymerization. In the present invention, in this case, the two-dimensional, graphite-based porous polymer, which is referred to as the present invention, is doped with a hetero atom, a metal or a metal oxide.
可由熟習此項技術者選擇本發明之二維、石墨基多孔聚合物之適合之分子量。 Suitable molecular weights for the two-dimensional, graphite-based porous polymers of the present invention can be selected by those skilled in the art.
在本發明之第二態樣中，本發明係關於一種自本發明之二維、石墨基多孔聚合物產生之多孔碳，較佳地其中多孔碳摻雜有來自二維、石墨基多孔聚合物之單體的雜原子。 In a second aspect of the invention, the invention relates to a porous carbon produced from a two-dimensional, graphite-based porous polymer of the invention, preferably wherein the porous carbon is doped with a two-dimensional, graphite-based porous polymer The hetero atom of the monomer.
在一較佳具體實例中，(可)藉由本發明之二維、石墨基多孔聚合物之直接熱解獲得本發明之多孔碳。 In a preferred embodiment, the porous carbon of the present invention is obtained by direct pyrolysis of a two-dimensional, graphite-based porous polymer of the present invention.
在本發明之一些具體實例中，(可)藉由本發明之希夫鹼型二維、石墨基多孔聚合物之直接熱解獲得本發明之石墨基多孔碳。當藉由穿透式電子顯微鏡(TEM)分析時，TEM影像中之交替暗明資訊表明此材料中存在多個孔，然而，由於劇烈分解，在熱解之後並非維持所有孔及通道。可藉由氮氣物理吸附量測進一步確認碳薄片之多孔性質。 In some embodiments of the invention, the graphite-based porous carbon of the present invention is obtained by direct pyrolysis of a Schiff base type two-dimensional, graphite-based porous polymer of the present invention. When analyzed by a transmission electron microscope (TEM), alternating dark information in the TEM image indicates the presence of multiple pores in the material, however, due to violent decomposition, not all pores and channels are maintained after pyrolysis. The porous nature of the carbon flakes can be further confirmed by nitrogen sorption measurement.
在本發明之一些其他具體實例中，(可)藉由本發明之石墨基共軛微孔聚合物之直接熱解獲得本發明之石墨基多孔碳。 In some other specific examples of the invention, the graphite-based porous carbon of the present invention is obtained by direct pyrolysis of the graphite-based conjugated microporous polymer of the present invention.
本發明之共軛微孔聚合物可為富含碳之前驅體類型，其可將雜原子、金屬或金屬氧化物併入至聚合物之碳架中以用於各種應用，諸如能量儲存及電化學催化。熱解重量分析(TGA)展示本發明之石墨基二維共軛微孔聚合物及共軛微孔聚合物(非石墨基)二者均可以諸如70%-90%之高碳產率可行地轉化成碳材料。 The conjugated microporous polymer of the present invention may be a carbon-rich precursor type that incorporates heteroatoms, metals or metal oxides into the carbon frame of the polymer for various applications such as energy storage and electrochemicalization. Learn catalysis. Thermogravimetric analysis (TGA) shows that both the graphite-based two-dimensional conjugated microporous polymer and the conjugated microporous polymer (non-graphite based) of the present invention can be used in a high carbon yield such as 70% to 90%. Converted to carbon material.
本發明之第三態樣係關於一種用於產生本發明之二維、石墨基多孔聚合物之方法，其包含以下步驟：A.氧化石墨烯以形成石墨烯氧化物；B.將石墨烯氧化物分散於溶劑中以形成分散液；C.添加單體至分散液及聚合單體以形成二維、石墨基多孔聚合物。 A third aspect of the invention relates to a method for producing a two-dimensional, graphite-based porous polymer of the invention comprising the steps of: A. graphene oxide to form graphene oxide; B. oxidation of graphene The material is dispersed in a solvent to form a dispersion; C. The monomer is added to the dispersion and the polymerized monomer to form a two-dimensional, graphite-based porous polymer.
上述單體適合於本發明之方法。 The above monomers are suitable for the process of the invention.
較佳地，在本發明之一個具體實例中，用於產生本發明之二維、石墨基多孔聚合物之方法包含以下步驟：A.氧化石墨烯以形成石墨烯氧化物；A1.用胺基官能化劑對石墨烯氧化物進行官能化以獲得官能化石墨烯氧化物；B.將官能化石墨烯氧化物分散於溶劑中以形成分散液；C.添加單體至分散液及聚合單體以形成本發明之二維、石墨基多孔聚合物。 Preferably, in one embodiment of the invention, the method for producing the two-dimensional, graphite-based porous polymer of the present invention comprises the steps of: A. graphene oxide to form graphene oxide; A1. using an amine group The functionalizing agent functionalizes the graphene oxide to obtain a functionalized graphene oxide; B. disperses the functionalized graphene oxide in a solvent to form a dispersion; C. adds the monomer to the dispersion and the polymerized monomer To form the two-dimensional, graphite-based porous polymer of the present invention.
用於本發明中之石墨烯可獲自任何適合之來源，諸如石墨。在本發明中，可藉由任何在此項技術中適合之方法氧化石墨烯。此外，適合於本發明之方法的溶劑可為有機溶劑，諸如二甲基甲醯胺 (DMF)、二甲亞碸(DMSO)、N-甲基吡咯啶酮(NMP)、N-乙基吡咯啶酮(NEP)、氯仿及甲苯。較佳地，適合於本發明之方法的溶劑為二甲基甲醯胺(DMF)。 The graphene used in the present invention can be obtained from any suitable source, such as graphite. In the present invention, graphene can be oxidized by any method suitable in the art. Further, the solvent suitable for the method of the present invention may be an organic solvent such as dimethylformamide (DMF), dimethyl hydrazine (DMSO), N-methylpyrrolidone (NMP), N-ethylpyrrolidone (NEP), chloroform and toluene. Preferably, the solvent suitable for the process of the invention is dimethylformamide (DMF).
在本發明之一些較佳具體實例中，所用含鹵素單體及炔烴單體可溶於本發明之方法中使用之溶劑中，較佳地，含二鹵素/三鹵素/四鹵素單體及二炔烴/三炔烴/四炔烴單體全部可溶於本發明之方法中使用之溶劑中。 In some preferred embodiments of the invention, the halogen-containing monomer and the alkyne monomer used are soluble in the solvent used in the process of the invention, preferably a dihalogen/trihalogen/tetrahalogen monomer and The diyne/triyne/tetrayne hydrocarbon monomers are all soluble in the solvent used in the process of the invention.
在本發明之方法中，用於聚合之聚合起始劑並非關鍵。熟習此項技術者可根據實際用途作出適當選擇。 In the process of the present invention, the polymerization initiator used for the polymerization is not critical. Those skilled in the art can make appropriate choices based on actual use.
在本發明之方法中，聚合催化劑可用於本發明之方法中。熟習此項技術者可根據實際用途作出關於聚合催化劑之適當選擇。舉例而言，在本發明之方法之一些具體實例中，可在聚合期間使用諸如Pd[0]基或Pd[II]基催化劑之催化劑。此外，在本發明之方法之一些具體實例中，在聚合期間使用共催化劑。舉例而言，在本發明之方法期間，可將CuI(或其可表示為Cu[I])用作共催化劑以活化炔烴基團。 In the process of the present invention, a polymerization catalyst can be used in the process of the present invention. Those skilled in the art can make appropriate choices regarding the polymerization catalyst depending on the actual use. For example, in some embodiments of the method of the invention, a catalyst such as a Pd[0] group or a Pd[II] based catalyst can be used during the polymerization. Moreover, in some embodiments of the method of the invention, a cocatalyst is used during the polymerization. For example, during the process of the invention, CuI (or it may be represented as Cu[I]) may be used as a cocatalyst to activate an alkyne group.
在本發明之一些具體實例中，可能不需要聚合催化劑。舉例而言，在本發明之方法之一些具體實例中，在產生本發明之希夫鹼型二維、石墨基多孔聚合物中不使用催化劑。 In some embodiments of the invention, a polymerization catalyst may not be required. For example, in some embodiments of the method of the present invention, no catalyst is used in producing the Schiff base type two-dimensional, graphite-based porous polymer of the present invention.
可在任何適當溫度及壓力下進行本發明之方法。在本發明之一些具體實例中，在0至200℃、較佳0至150℃或10至100℃之間的溫度及1-10標準大氣壓、較佳1-5標準大氣壓、諸如2-3標準大氣壓之間的壓力下使添加至本發明之方法之添加單體聚合。 The process of the invention can be carried out at any suitable temperature and pressure. In some embodiments of the invention, the temperature is between 0 and 200 ° C, preferably between 0 and 150 ° C or between 10 and 100 ° C and between 1 and 10 standard atmospheres, preferably between 1 and 5 standard atmospheres, such as 2-3. The additional monomer added to the process of the invention is polymerized under pressure between atmospheric pressures.
在一較佳具體實例中，在步驟A之後且在步驟B之前，本發明之方法進一步包含步驟 In a preferred embodiment, the method of the present invention further comprises the steps after step A and before step B.
A1.用官能化劑對石墨烯氧化物進行官能化以形成官能化石墨烯氧化物。 A1. Functionalizing a graphene oxide with a functionalizing agent to form a functionalized graphene oxide.
較佳地，官能化劑係選自由以下組成之群：胺基官能化劑及溴基官能化劑及還原劑；更佳地，在藉由溴基官能化劑對石墨烯氧化物進行官能化之前，藉由還原劑對石墨烯氧化物進行還原。舉例而言，胺基官能化石墨烯氧化物可適合於獲得本發明之希夫鹼型二維、石墨基多孔聚合物，且溴基官能化還原石墨烯氧化物可適合於獲得本發明之二維、石墨基共軛多孔聚合物。適合之胺基官能化劑包括所有高度可溶二胺基分子，諸如1,3-二胺基丙烷、乙二胺、1,4-二胺基丁烷。適合之溴基官能化劑可為任何適合於本發明之目的之溴基官能化劑，諸如4-溴苯基四氟硼酸重氮鹽。適合之還原劑可為任何適合於本發明之目的之還原劑，諸如單水合肼、硼氫化鈉及維生素B12。 Preferably, the functionalizing agent is selected from the group consisting of an amine functionalizing agent and a bromine functionalizing agent and a reducing agent; more preferably, the graphene oxide is functionalized by a bromine functionalizing agent. Previously, the graphene oxide was reduced by a reducing agent. For example, an amine functionalized graphene oxide may be suitable for obtaining a Schiff base type two-dimensional, graphite-based porous polymer of the present invention, and a bromine-functionalized reduced graphene oxide may be suitable for obtaining the second aspect of the present invention. Dimensional, graphite-based conjugated porous polymer. Suitable amine functionalizers include all highly soluble diamine based molecules such as 1,3-diaminopropane, ethylenediamine, 1,4-diaminobutane. Suitable bromo-functionalizing agents can be any bromo-functionalizing agent suitable for the purposes of the present invention, such as the 4-bromophenyltetrafluoroborate diazonium salt. Suitable reducing agents can be any reducing agent suitable for the purposes of the present invention, such as hydrazine monohydrate, sodium borohydride and vitamin B12.
在本發明之方法中，在聚合期間，官能化石墨烯比非官能化石墨烯更容易得多地分散於有機溶劑(諸如DMF及DMSO)中及與單體反應。因此，相比於非官能化石墨烯之表面，在官能化石墨烯之表面上更容易進行聚合，且維持具有較大縱橫比之石墨烯之形態。多孔聚合物之二維結構可源自在以一鍋法聚合期間併入之官能化石墨烯。 In the process of the present invention, functionalized graphene is more easily dispersed in organic solvents (such as DMF and DMSO) and reacted with the monomers during polymerization than during non-functionalized graphene. Therefore, the polymerization is more easily carried out on the surface of the functionalized graphene than on the surface of the non-functionalized graphene, and the morphology of the graphene having a large aspect ratio is maintained. The two-dimensional structure of the porous polymer can be derived from functionalized graphene incorporated during one-pot polymerization.
不希望受任何理論束縛，咸信官能化石墨烯用作用於石墨烯表面上之聚合之二維模板。特定言之，咸信本發明中之石墨烯氧化物及/或官能化石墨烯氧化物用作模板，導引具有二維形態的本發明之多孔聚合 物，諸如本發明之希夫鹼型二維、石墨基多孔聚合物及二維、石墨基共軛多孔聚合物之生長。 Without wishing to be bound by any theory, the salt-functionalized graphene is used as a two-dimensional template for polymerization on the surface of graphene. In particular, the graphene oxide and/or the functionalized graphene oxide of the present invention is used as a template to guide the porous polymerization of the present invention having a two-dimensional morphology. The growth of a two-dimensional, graphite-based porous polymer such as the Schiff base of the present invention and a two-dimensional, graphite-based conjugated porous polymer.
在本發明中，基於噻吩、噻唑及吡啶之雜環單體可用於藉助於金屬催化之薗頭-萩原偶合反應(Sonogashira-Hagihara coupling reaction)在石墨烯表面上與1,3,5-三乙炔基苯單體聚合以獲得本發明之二維、石墨基多孔聚合物。舉例而言，在本發明之一些較佳具體實例中，在無水DMF中將含有硫及/或氮雜環的基於噻吩、噻唑及吡啶之含鹵素之單體與炔烴單體(諸如1,3,5-三乙炔基苯)及溴基官能化還原石墨烯氧化物混合，接著密封且在薗頭-萩原反應條件下反應以獲得本發明之二維、石墨基多孔聚合物。大部分鈀基催化劑適合於薗頭偶合反應，諸如肆(三苯基膦)鈀、1,1'-雙(二苯基膦基)二茂鐵二氯化鈀、乙酸鈀(II)等。 In the present invention, a heterocyclic monomer based on thiophene, thiazole and pyridine can be used on a graphene surface with 1,3,5-triacetylene by means of a metal-catalyzed Sonogashira-Hagihara coupling reaction. The phenyl monomer is polymerized to obtain a two-dimensional, graphite-based porous polymer of the present invention. For example, in some preferred embodiments of the present invention, a halogen-containing monomer based on thiophene, thiazole, and pyridine containing a sulfur and/or a nitrogen heterocycle is combined with an alkyne monomer (such as 1, in anhydrous DMF). The 3,5-triethynylbenzene) and the bromine-functionalized reduced graphene oxide are mixed, then sealed and reacted under the reaction of the taro-retinol to obtain the two-dimensional, graphite-based porous polymer of the present invention. Most palladium-based catalysts are suitable for the taro coupling reaction, such as ruthenium (triphenylphosphine) palladium, 1,1'-bis(diphenylphosphino)ferrocene palladium dichloride, palladium (II) acetate, and the like.
在本發明之一個較佳具體實例中，用於產生本發明之二維、石墨基共軛多孔聚合物之方法包含以下步驟： In a preferred embodiment of the invention, the method for producing a two-dimensional, graphite-based conjugated porous polymer of the invention comprises the steps of:
A.還原石墨烯氧化物或石墨烯以形成還原之石墨烯氧化物或還原之石墨烯； A1.用官能化劑對還原之石墨烯氧化物或還原之石墨烯進行官能化以形成官能化還原石墨烯氧化物或官能化還原石墨烯，官能化劑較佳為溴基官能化劑。 A. reducing graphene oxide or graphene to form reduced graphene oxide or reduced graphene; A1. The reduced graphene oxide or reduced graphene is functionalized with a functionalizing agent to form a functionalized reduced graphene oxide or functionalized reduced graphene, preferably a bromine-based functionalizing agent.
B.將官能化還原石墨烯氧化物或官能化還原石墨烯分散於溶劑中以形成分散液； B. dispersing the functionalized reduced graphene oxide or the functionalized reduced graphene in a solvent to form a dispersion;
C.添加單體至分散液且將單體聚合成二維、石墨基共軛多孔聚合物。 C. Adding a monomer to the dispersion and polymerizing the monomer into a two-dimensional, graphite-based conjugated porous polymer.
在本發明之另一較佳具體實例中，用於產生本發明之希夫鹼型二維、石墨基多孔聚合物之方法包含以下步驟：A.氧化石墨烯以形成石墨烯氧化物；A1.用胺基官能化劑對石墨烯氧化物進行官能化以獲得官能化石墨烯氧化物；B.將官能化石墨烯氧化物分散於溶劑中以形成分散液；C.添加單體至分散液且將單體聚合成本發明之希夫鹼型二維、石墨基多孔聚合物。 In another preferred embodiment of the present invention, the method for producing the Schiff base type two-dimensional, graphite-based porous polymer of the present invention comprises the steps of: A. graphene oxide to form graphene oxide; A1. Functionalizing the graphene oxide with an amine functionalizing agent to obtain a functionalized graphene oxide; B. dispersing the functionalized graphene oxide in a solvent to form a dispersion; C. adding a monomer to the dispersion and The monomer is polymerized into the Schiff base type two-dimensional, graphite-based porous polymer of the invention.
在本發明中，基於N2吸附在ASAP 2010 M/C表面積及孔隙率測定分析器(Micromeritics Instrument公司，USA)上量測本發明之多孔聚合物之布魯諾爾-艾美特-泰勒(Brunauer-Emment-Teller；BET)比表面積。本發明之二維多孔聚合物顯示長度及寬度為0.2-3μm且厚度為10-50nm之典型薄片形態，且此等聚合物網狀物之BET表面積可在458與888m2 g-1之間變化。希夫鹼型二維、石墨基多孔聚合物顯示長度及寬度為0.2-2μm且厚度為10-250nm之典型薄片形態，且此等聚合物網狀物之BET表面積為330-900m2 g-1。所有二維多孔聚合物之孔寬度均小於2nm，其為典型微孔。 In the present invention, Brunauer-Emment- of the porous polymer of the present invention is measured based on N 2 adsorption on an ASAP 2010 M/C surface area and porosity analyzer (Micromeritics Instrument, USA). Teller; BET) specific surface area. The two-dimensional porous polymer of the present invention exhibits a typical sheet morphology having a length and width of 0.2 to 3 μm and a thickness of 10 to 50 nm, and the BET surface area of such polymer webs can vary between 458 and 888 m 2 g -1 . . The Schiff base type two-dimensional, graphite-based porous polymer exhibits a typical sheet morphology having a length and a width of 0.2 to 2 μm and a thickness of 10 to 250 nm, and the BET surface area of the polymer network is 330-900 m 2 g -1 . All two-dimensional porous polymers have pore widths of less than 2 nm, which are typical micropores.
本發明之第四態樣係關於一種本發明之二維、石墨基多孔聚合物之用途，其用於光捕獲、感測、氣體分離及儲存、催化及能量儲存及轉化中。 A fourth aspect of the invention relates to the use of a two-dimensional, graphite-based porous polymer of the invention for use in light capture, sensing, gas separation and storage, catalysis and energy storage and conversion.
本發明之第四態樣係關於一種本發明之多孔碳之用途，其用於製造電化學雙層電容器或者稱為超級電容器。 A fourth aspect of the invention relates to the use of a porous carbon of the invention for the manufacture of an electrochemical double layer capacitor or as a supercapacitor.
本發明具有多種優勢，舉例而言， The invention has several advantages, for example,
1.可以大規模製備本發明中使用之官能化石墨烯模板，因為可以公斤規模製備前驅體石墨烯氧化物。適合之單體全部為市售的且極廉價。 1. The functionalized graphene template used in the present invention can be prepared on a large scale because the precursor graphene oxide can be prepared on a kilogram scale. Suitable monomers are all commercially available and extremely inexpensive.
2.在本發明中，二維、石墨基多孔聚合物及二維、石墨基多孔碳之二維形態可藉由使用官能化石墨烯容易地控制且可以大規模合成。二維、石墨基多孔碳為二維石墨基多孔聚合物在不使用任何無機多孔模板之情況下的直接熱解產物。相比於在不使用石墨烯模板之情況下衍生自多孔聚合物之多孔碳的電化學雙層電容，本發明之二維石墨基多孔碳之電化學雙層電容經改良。 2. In the present invention, the two-dimensional, graphite-based porous polymer and the two-dimensional form of two-dimensional, graphite-based porous carbon can be easily controlled by using functionalized graphene and can be synthesized on a large scale. The two-dimensional, graphite-based porous carbon is a direct pyrolysis product of a two-dimensional graphite-based porous polymer without using any inorganic porous template. The electrochemical double layer capacitance of the two-dimensional graphite-based porous carbon of the present invention is improved compared to the electrochemical double layer capacitance of porous carbon derived from a porous polymer without using a graphene template.
3.產生之二維石墨基多孔聚合物共價附著至石墨烯表面上，因此極穩定且可容易以大規模合成。 3. The resulting two-dimensional graphite-based porous polymer is covalently attached to the graphene surface, and thus is extremely stable and can be easily synthesized on a large scale.
4.本發明提供一種用於製備二維石墨基多孔聚合物之原位方法。 4. The present invention provides an in situ process for preparing a two-dimensional graphite-based porous polymer.
5.本發明之二維石墨基多孔碳係藉助於直接高溫熱解由本發明之二維石墨基多孔聚合物產生而無需使用任何無機多孔模板，且當然無需任何其他處理以移除無機多孔模板，因此本發明之方法為簡單且環境友好的。 5. The two-dimensional graphite-based porous carbon of the present invention is produced by the direct high-temperature pyrolysis from the two-dimensional graphite-based porous polymer of the present invention without using any inorganic porous template, and of course without any other treatment to remove the inorganic porous template. Thus, the method of the invention is simple and environmentally friendly.
6.石墨烯表面上分佈之孔之孔寬度比衍生自多孔聚合物之正常多孔碳之孔寬度分佈得更窄。 6. The pore width of the pores distributed on the surface of the graphene is narrower than the pore width of the normal porous carbon derived from the porous polymer.
7.相比於在不使用石墨烯模板之情況下衍生自多孔聚合物之多孔碳之電化學雙層電容，二維石墨基多孔碳之電化學雙層電容經改良。 7. The electrochemical double layer capacitance of two-dimensional graphite-based porous carbon is improved compared to the electrochemical double layer capacitance of porous carbon derived from a porous polymer without using a graphene template.
特定言之，本發明係關於以下具體實例。 In particular, the present invention relates to the following specific examples.
1.一種二維、石墨基多孔聚合物，其中石墨烯層包夾於該多孔聚合物之間，該多孔聚合物較佳為微孔的，該石墨烯層較佳藉由共價鍵包夾於 該多孔聚合物之間。 A two-dimensional, graphite-based porous polymer, wherein a graphene layer is sandwiched between the porous polymers, the porous polymer is preferably microporous, and the graphene layer is preferably sandwiched by a covalent bond to Between the porous polymers.
2.如具體實例1之二維、石墨基多孔聚合物，其中該多孔聚合物呈網狀物形式，該石墨烯藉由共價鍵包夾於該多孔聚合物之間。 2. The two-dimensional, graphite-based porous polymer of embodiment 1, wherein the porous polymer is in the form of a network, the graphene being sandwiched between the porous polymers by covalent bonding.
3.如具體實例1或2之二維、石墨基多孔聚合物，其中該多孔聚合物係由選自由以下各者組成之群之單體聚合產生：含鹵素型單體、炔烴型單體、含胺基型單體及醛型單體。 3. The two-dimensional, graphite-based porous polymer of the specific example 1 or 2, wherein the porous polymer is produced by polymerization of a monomer selected from the group consisting of halogen-containing monomers and alkyne monomers. , an amine group-containing monomer and an aldehyde type monomer.
4.如具體實例1至3中任一項之二維、石墨基多孔聚合物，其中該多孔聚合物係由以AmBn形式混合之兩種不同類型單體之混合物之聚合產生，其中A及B分別表示選自由以下各者組成之群的單體類型：含鹵素型單體、炔烴型單體、含胺基型單體及醛型單體，且m為參與單體A中之聚合之官能基之數目，且n為參與單體B中之聚合之官能基之數目，且其中m>n2或n>m2或n=m>2。 4. The two-dimensional, graphite-based porous polymer of any one of embodiments 1 to 3, wherein the porous polymer is produced by polymerization of a mixture of two different types of monomers mixed in the form of A m B n , wherein A and B respectively represent a monomer type selected from the group consisting of a halogen-containing monomer, an alkyne-type monomer, an amine-containing monomer, and an aldehyde-type monomer, and m is a participating monomer A. The number of functional groups polymerized, and n is the number of functional groups participating in the polymerization in monomer B, and wherein m>n 2 or n>m 2 or n=m>2.
5.如具體實例1至4中任一項之二維、石墨基多孔聚合物，其中該多孔聚合物為二維、石墨基共軛多孔聚合物或希夫鹼型二維、石墨基多孔聚合物。 5. The two-dimensional, graphite-based porous polymer according to any one of embodiments 1 to 4, wherein the porous polymer is a two-dimensional, graphite-based conjugated porous polymer or a Schiff base type two-dimensional, graphite-based porous polymerization. Things.
6.如具體實例5之二維、石墨基多孔聚合物，其中該二維、石墨基共軛多孔聚合物係由根據AmBn模式混合之鹵素型單體及炔烴型單體，諸如二溴型單體及三炔烴單體，或三溴型單體及二炔烴單體，或四溴型單體及二炔烴單體之混合物的聚合產生，其中AmBn具有與具體實例4中所定義相同之含義。 6. The two-dimensional, graphite-based porous polymer of Specific Example 5, wherein the two-dimensional, graphite-based conjugated porous polymer is a halogen-type monomer and an alkyne-type monomer mixed according to an A m B n mode, such as Dibromo-type monomer and tri-alkyne monomer, or tribromo-type monomer and di-alkyne monomer, or a mixture of a tetra-bromo-type monomer and a di-alkyne monomer, wherein A m B n has The same meaning is defined in Concrete Example 4.
7.如具體實例5之二維、石墨基多孔聚合物，其中該希夫鹼型二維、石墨基多孔聚合物係由根據AmBn模式混合之醛型單體及含胺基型單 體，諸如二醛型單體及三胺型單體，或三醛型單體及三胺型單體，或三醛型單體及二胺型單體，或三聚氰胺及二醛型單體之混合物的聚合產生，其中AmBn具有與具體實例4中所定義相同之含義，較佳地，希夫鹼型二維、石墨基多孔聚合物係由三聚氰胺及二醛型單體，諸如1,3-苯二醛、1,4-苯二醛、2,5-噻吩二醛、4,4'-聯苯二醛及2,6-吡啶二醛之混合物的聚合產生。 7. The two-dimensional, graphite-based porous polymer according to the specific example 5, wherein the Schiff base type two-dimensional, graphite-based porous polymer is composed of an aldehyde type monomer and an amine group-containing single type mixed according to the A m B n mode. a body, such as a dialdehyde type monomer and a triamine type monomer, or a trialdehyde type monomer and a triamine type monomer, or a trialdehyde type monomer and a diamine type monomer, or a melamine and a dialdehyde type monomer The polymerization of the mixture is produced, wherein A m B n has the same meaning as defined in the specific example 4, preferably, the Schiff base type two-dimensional, graphite-based porous polymer is composed of melamine and a dialdehyde type monomer such as 1 Polymerization of a mixture of 3-benzenedialdehyde, 1,4-benzenedialdehyde, 2,5-thiophenedialdehyde, 4,4'-biphenyldialdehyde and 2,6-pyridinedialdehyde.
8.一種由如具體實例1至7中任一項之二維、石墨基多孔聚合物產生之多孔碳，其較佳藉由該等二維、石墨基多孔聚合物之直接熱解產生。 8. A porous carbon produced by a two-dimensional, graphite-based porous polymer according to any one of embodiments 1 to 7, which is preferably produced by direct pyrolysis of the two-dimensional, graphite-based porous polymers.
9.如具體實例8之多孔碳，其中該多孔碳摻雜有雜原子，該雜原子較佳選自由以下組成之群：O、N、S及鹵素，諸如Cl或Br。 9. The porous carbon of embodiment 8, wherein the porous carbon is doped with a hetero atom, and the hetero atom is preferably selected from the group consisting of O, N, S, and a halogen such as Cl or Br.
10.一種用於產生如具體實例1至7中任一項之二維、石墨基多孔聚合物之方法，其包含：A.氧化石墨烯以形成石墨烯氧化物；B.將該石墨烯氧化物分散於溶劑中以形成分散液；C.添加單體至該分散液且將該單體聚合為該等二維、石墨基多孔聚合物，該單體較佳係藉助於縮合，諸如醛-胺基縮合，或藉助於偶合反應，諸如薗頭偶合反應聚合。 10. A method for producing a two-dimensional, graphite-based porous polymer according to any one of embodiments 1 to 7, comprising: A. graphene oxide to form a graphene oxide; B. oxidizing the graphene Dispersing in a solvent to form a dispersion; C. adding a monomer to the dispersion and polymerizing the monomer into the two-dimensional, graphite-based porous polymer, preferably by means of condensation, such as aldehyde- The amine group is condensed or polymerized by means of a coupling reaction such as a taro coupling reaction.
11.如具體實例10之方法，其中在步驟A之後且在步驟B之前，該方法進一步包含步驟 11. The method of embodiment 10, wherein after step A and prior to step B, the method further comprises the step
A1.用官能化劑對該石墨烯氧化物進行官能化以形成官能化石墨烯氧化物，該官能化劑較佳選自由以下組成之群：胺基官能化劑、溴基官能化劑及還原劑；更佳地，在該石墨烯氧化物經溴基官能化劑官能化之前，藉由還原劑還原該石墨烯氧化物，該胺基官能化劑較佳選自由以下組成之 群：所有高度可溶二胺基分子，諸如1,3-二胺基丙烷、乙二胺、1,4-二胺基丁烷；溴基官能化劑較佳為4-溴苯基四氟硼酸重氮鹽；且較佳地，該還原劑係選自由以下組成之群：單水合肼、硼氫化鈉及維生素B12。 A1. Functionalizing the graphene oxide with a functionalizing agent to form a functionalized graphene oxide, the functionalizing agent preferably being selected from the group consisting of an amine functionalizing agent, a bromine functionalizing agent, and a reduction More preferably, the graphene oxide is reduced by a reducing agent prior to functionalization of the graphene oxide with a bromine-based functionalizing agent, preferably selected from the group consisting of Group: all highly soluble diamine-based molecules, such as 1,3-diaminopropane, ethylenediamine, 1,4-diaminobutane; the bromine-functionalizing agent is preferably 4-bromophenyltetrafluoro a diazonium borate; and preferably, the reducing agent is selected from the group consisting of hydrazine monohydrate, sodium borohydride, and vitamin B12.
12.如具體實例10或11之方法，其中該單體係選自由以下組成之群：含鹵素型單體、炔烴型單體、含胺基型單體及醛型單體，該單體較佳為以AmBn形式混合的兩種不同類型單體之混合物，其中A及B分別表示選自由以下各者組成之群的單體類型：含鹵素型單體、炔烴型單體、含胺基型單體及醛型單體，m為參與單體A中之聚合之官能基之數目，且n為參與單體B中之聚合之官能基之數目，且其中m>n2或n>m2或n=m>2。 12. The method of embodiment 10 or 11, wherein the single system is selected from the group consisting of halogen-containing monomers, alkyne-type monomers, amine-containing monomers, and aldehyde-type monomers, the monomer Preferably, a mixture of two different types of monomers mixed in the form of A m B n , wherein A and B respectively represent a monomer type selected from the group consisting of halogen-containing monomers, alkyne monomers , an amine group-containing monomer and an aldehyde type monomer, m is the number of functional groups participating in the polymerization in the monomer A, and n is the number of functional groups participating in the polymerization in the monomer B, and wherein m>n 2 or n>m 2 or n=m>2.
13.一種用於產生如具體實例5之二維、石墨基共軛多孔聚合物之方法，其包含以下步驟：A.用還原劑還原石墨烯氧化物或石墨烯以形成還原之石墨烯氧化物或還原之石墨烯，該還原劑較佳選自由以下組成之群：單水合肼、硼氫化鈉及維生素B12；A1.用官能化劑對該還原石墨烯氧化物或該還原石墨烯進行官能化以形成官能化還原石墨烯氧化物或官能化還原石墨烯，該官能化劑較佳選自由以下組成之群：胺基官能化劑及溴基官能化劑，該官能化劑更佳為溴基官能化劑；B.將該官能化還原石墨烯氧化物或該官能化還原石墨烯分散於溶劑中以形成分散液；C.添加單體至該分散液且將該單體聚合為該二維、石墨基共軛多孔聚合物，較佳地，該單體係藉助於縮合，諸如醛-胺基縮合，或藉助於偶合 反應，諸如薗頭偶合反應聚合。 13. A method for producing a two-dimensional, graphite-based conjugated porous polymer as in Example 5, comprising the steps of: A. reducing a graphene oxide or graphene with a reducing agent to form a reduced graphene oxide Or reduced graphene, the reducing agent is preferably selected from the group consisting of hydrazine monohydrate, sodium borohydride and vitamin B12; A1. functionalizing the reduced graphene oxide or the reduced graphene with a functionalizing agent To form a functionalized reduced graphene oxide or a functionalized reduced graphene, the functionalizing agent is preferably selected from the group consisting of an amine functionalizing agent and a bromine functionalizing agent, and the functionalizing agent is more preferably a bromine group. a functionalizing agent; B. dispersing the functionalized reduced graphene oxide or the functionalized reduced graphene in a solvent to form a dispersion; C. adding a monomer to the dispersion and polymerizing the monomer into the two-dimensional a graphite-based conjugated porous polymer, preferably, the single system by means of condensation, such as aldehyde-amine condensation, or by means of coupling The reaction, such as a taro coupling reaction, is carried out.
14.如具體實例13之方法，其中該單體為根據AmBn模式混合之鹵素型單體及炔烴型單體，諸如二溴型單體及三炔烴單體，或三溴型單體及二炔烴單體，或四溴型單體及二炔烴單體之混合物，其中AmBn具有與具體實例12中所定義相同之含義。 14. The method of embodiment 13, wherein the monomer is a halogen-type monomer and an alkyne-type monomer mixed according to the A m B n mode, such as a dibromo-type monomer and a tri-alkyne monomer, or a tribromo-type a monomer and a diacetylene monomer, or a mixture of a tetrabromo-type monomer and a di-alkyne monomer, wherein A m B n has the same meaning as defined in the specific example 12.
15.一種用於產生如具體實例5之希夫鹼型二維、石墨基多孔聚合物之方法，其包含以下步驟：A.氧化石墨烯以形成石墨烯氧化物；A1.用胺基官能化劑對該石墨烯氧化物進行官能化以獲得官能化石墨烯氧化物；B.將該官能化石墨烯氧化物分散於溶劑中以形成分散液；C.添加單體至該分散液且將該單體聚合為該等希夫鹼型二維、石墨基多孔聚合物，較佳地，該單體係藉助於縮合，諸如醛-胺基縮合，或藉助於偶合反應，諸如薗頭偶合反應聚合。 15. A method for producing a Schiff base type two-dimensional, graphite-based porous polymer as in Example 5, comprising the steps of: A. graphene oxide to form a graphene oxide; A1. functionalizing with an amine group The graphene oxide is functionalized to obtain a functionalized graphene oxide; B. the functionalized graphene oxide is dispersed in a solvent to form a dispersion; C. adding a monomer to the dispersion and The monomer is polymerized into the Schiff base type two-dimensional, graphite-based porous polymer. Preferably, the single system is polymerized by means of condensation, such as aldehyde-amine condensation, or by means of a coupling reaction, such as a taro coupling reaction. .
16.如具體實例15之方法，其中該單體為根據AmBn模式混合之醛型單體及含胺基型單體，諸如二醛型單體及三胺型單體，或三醛型單體及三胺型單體，或三醛型單體及二胺型單體，或三聚氰胺及二醛型單體之混合物，其中AmBn具有與具體實例12中所定義相同之含義，較佳地，該單體為三聚氰胺及二醛型單體，諸如1,3-苯二醛、1,4-苯二醛、2,5-噻吩二醛、4,4'-聯苯二醛及2,6-吡啶二醛之混合物。 16. The method of embodiment 15, wherein the monomer is an aldehyde type monomer and an amine group type monomer mixed according to the A m B n mode, such as a dialdehyde type monomer and a triamine type monomer, or a trialdehyde Type monomer and triamine type monomer, or trialdehyde type monomer and diamine type monomer, or a mixture of melamine and dialdehyde type monomers, wherein A m B n has the same meaning as defined in specific example 12. Preferably, the monomer is a melamine and a dialdehyde type monomer such as 1,3-benzenedialdehyde, 1,4-benzenedialdehyde, 2,5-thiophenedialdehyde, 4,4'-biphenyldiene a mixture of an aldehyde and 2,6-pyridinedialdehyde.
17.一種如具體實例1至7中任一項之二維、石墨基多孔聚合物之用途，其用於光捕獲、感測、氣體分離及儲存、催化及能量儲存及轉化中。 17. Use of a two-dimensional, graphite-based porous polymer according to any of embodiments 1 to 7 for light capture, sensing, gas separation and storage, catalysis and energy storage and conversion.
18.一種如具體實例8或9之多孔碳之用途，其用於製造電容、較佳電化學雙層電容器或超級電容器。 18. Use of a porous carbon as in Example 8 or 9 for the manufacture of a capacitor, preferably an electrochemical double layer capacitor or a supercapacitor.
實施例 Example
將參考特定實施例在下文中進一步說明本發明，該等特定實施例僅為例示性及解釋性的且不為限制性的。 The invention is further described below with reference to the particular embodiments, which are merely illustrative and illustrative and not restrictive.
當使用各份數及百分比時，若未另外規定，則以重量計提供。 When parts and percentages are used, they are provided by weight unless otherwise specified.
實施例1.本發明之二維石墨基共軛多孔聚合物及二維石墨基多孔碳之製備，及其對照樣品之製備 Example 1. Preparation of two-dimensional graphite-based conjugated porous polymer of the present invention and two-dimensional graphite-based porous carbon, and preparation of the same
製備A. Preparation A.
藉由溴基官能化還原石墨烯氧化物(RGBr)、芳基伸乙炔基及芳基鹵之鈀催化薗頭-萩原交叉偶合反應合成二維網狀物(石墨基二維共軛微孔聚合物，GMP)。 Synthesis of two-dimensional network by graphite-based two-dimensional conjugated microporous polymer by bromo-functionalized reduction of graphene oxide (RGBr), aryl ethynyl group and aryl halide palladium-catalyzed taro-ruthenium cross-coupling reaction , GMP).
首先，將RGBr(65mg)在無水DMF(100mL)中進行音波處理直至完全分散。隨後，將1,3,5-三乙炔基苯(300mg，2.0mmol)、2,5-二溴噻吩(484mg，2.0mmol)、肆-(三苯基膦)鈀(35mg，0.03mmol)、碘化亞銅(7mg，0.03mmol)及Et3N(4mL)溶解於RGBr分散液中。將反應混合物加熱至80℃，在氬氣氛圍下攪拌72h。隨後，將不溶沈澱網狀聚合物過濾且分別用氯仿、水、丙酮及THF洗滌四次以移除任何未反應之單體或催化劑殘餘物。另外，藉由用丙酮進行索氏萃取(Soxhlet extraction)進一步純化聚合物48h。將產物在60℃下於真空中乾燥24h且磨碎為精細黑色粉末以獲得含硫石墨基二維共軛微孔聚合物(GMP-S)。 First, RGBr (65 mg) was sonicated in anhydrous DMF (100 mL) until completely dispersed. Subsequently, 1,3,5-triethynylbenzene (300 mg, 2.0 mmol), 2,5-dibromothiophene (484 mg, 2.0 mmol), hydrazine-(triphenylphosphine)palladium (35 mg, 0.03 mmol), Cuprous iodide (7 mg, 0.03 mmol) and Et 3 N (4 mL) were dissolved in RGBr dispersion. The reaction mixture was heated to 80 ° C and stirred under argon for 72 h. Subsequently, the insoluble precipitated network polymer was filtered and washed four times with chloroform, water, acetone and THF, respectively, to remove any unreacted monomer or catalyst residue. Further, the polymer was further purified by Soxhlet extraction with acetone for 48 h. The product was dried in vacuum at 60 ° C for 24 h and ground to a fine black powder to obtain a sulfur-containing graphite-based two-dimensional conjugated microporous polymer (GMP-S).
將如此製成的二維多孔聚合物，含硫石墨基二維共軛微孔聚合物(GMP-S)在800℃下於氬氣氛圍下熱解2h以獲得二維多孔碳，亦即含硫石墨基二維中孔碳(表示為GMC-S)。 The two-dimensional porous polymer thus prepared, the sulfur-containing graphite-based two-dimensional conjugated microporous polymer (GMP-S) is pyrolyzed at 800 ° C for 2 h under an argon atmosphere to obtain two-dimensional porous carbon, that is, Sulfur graphite based two-dimensional mesoporous carbon (expressed as GMC-S).
除了不使用溴基官能化還原石墨烯氧化物(RGBr)之外，藉由與上文所述相同之程序合成對照樣品含硫共軛微孔聚合物(MP-S，非石墨基)。 A control sample sulfur-containing conjugated microporous polymer (MP-S, non-graphite based) was synthesized by the same procedure as described above except that bromo functionalized reduced graphene oxide (RGBr) was not used.
藉由與上文關於產生GMC-S所述相同之程序自含硫共軛微孔聚合物(MP-S)製備對照樣品含硫中孔碳(MC-S)。 Control sample sulfur-containing mesoporous carbon (MC-S) was prepared from sulfur-containing conjugated microporous polymer (MP-S) by the same procedure as described above for the production of GMC-S.
製備B. Preparation B.
藉由根據W.S.J.Hummers,R.E.Offeman,J.Am.Chem.Soc.1958,80,1339之經改質Hummers法自天然石墨薄片合成石墨烯氧化物(GO)，且接著在回流下在十二烷基苯磺酸鈉存在下藉由水合肼還原。將如此製成的界面活性劑包覆之還原石墨烯氧化物(RGO)冷卻至室溫。藉由在最小量之水(重氮鹽完全溶解即刻量測到之量)中預溶解固體重氮鹽(5當量)，且接著將獲得之溶液伴以攪拌逐滴添加至還原石墨烯氧化物(RGO)分散液中進行官能化。在於室溫下攪拌1小時之後，隨後將混合物倒入至丙酮中。藉由過濾及分別用水、丙酮及DMF洗滌三次對如此製成之溴基官能化還原石墨烯氧化物(RGBr)進行純化。經純化之如此製成的溴基官能化還原石墨烯氧化物(RGBr)在使用之前經真空乾燥。 Synthesis of graphene oxide (GO) from natural graphite flakes by modified Hummers method according to WSJ Hummers, REOffeman, J. Am. Chem. Soc. 1958, 80 , 1339, and then under reflux in dodecylbenzene Reduction by hydrazine hydrate in the presence of sodium sulfonate. The surfactant-coated reduced graphene oxide (RGO) thus prepared was cooled to room temperature. The solid diazonium salt (5 equivalents) is pre-dissolved in a minimum amount of water (the amount immediately measured by complete dissolution of the diazonium salt), and then the obtained solution is added dropwise to the reduced graphene oxide with stirring. Functionalization in the (RGO) dispersion. After stirring at room temperature for 1 hour, the mixture was then poured into acetone. The bromo-functionalized reduced graphene oxide (RGBr) thus produced was purified by filtration and washing three times with water, acetone and DMF, respectively. The brominated functionalized reduced graphene oxide (RGBr) thus produced was purified by vacuum drying before use.
藉由(RGBr)、1,3,5-三乙炔基苯及芳基鹵(2,5-二溴噻吩、2,5-二溴-1,3-噻唑及2,6-二溴吡啶)之鈀催化薗頭-萩原交叉偶合反應建立GMP(石墨基二維共軛微孔聚合物)。在下文中給出代表性實驗程序(用 於含硫石墨基二維共軛微孔聚合物(GMP-S))。 By (RGBr), 1,3,5-triacetylenylbenzene and aryl halides (2,5-dibromothiophene, 2,5-dibromo-1,3-thiazole and 2,6-dibromopyridine) The palladium-catalyzed taro-萩 original cross-coupling reaction establishes GMP (graphite-based two-dimensional conjugated microporous polymer). Representative experimental procedures are given below A sulfur-containing graphite-based two-dimensional conjugated microporous polymer (GMP-S)).
首先，將RGBr(65mg)在無水DMF(100mL)中進行音波處理直至完全分散。隨後，將1,3,5-三乙炔基苯(300mg，2.0mmol)、2,5-二溴噻吩(484mg，2.0mmol)、肆-(三苯基膦)鈀(35mg，0.03mmol)、碘化亞銅(7mg，0.03mmol)及Et3N(4mL)添加至(RGBr)分散液中。將反應混合物加熱至80℃，且在氬氣氛圍下攪拌72h。隨後，將不溶沈澱聚合物網狀物過濾且分別用氯仿、水、丙酮及THF洗滌四次以移除任何未反應之單體或催化劑殘餘物。藉由用丙酮進行索氏萃取進一步純化聚合物網狀物48h。將產物在真空中於60℃下乾燥24h，且研磨成精細黑色粉末。在不包含RGBr的情況下藉由相同程序合成對照樣品(含硫共軛微孔聚合物(MP-S，非石墨基))。 First, RGBr (65 mg) was sonicated in anhydrous DMF (100 mL) until completely dispersed. Subsequently, 1,3,5-triethynylbenzene (300 mg, 2.0 mmol), 2,5-dibromothiophene (484 mg, 2.0 mmol), hydrazine-(triphenylphosphine)palladium (35 mg, 0.03 mmol), Cuprous iodide (7 mg, 0.03 mmol) and Et 3 N (4 mL) were added to the (RGBr) dispersion. The reaction mixture was heated to 80 ° C and stirred under argon for 72 h. Subsequently, the insoluble precipitated polymer network was filtered and washed four times with chloroform, water, acetone and THF, respectively, to remove any unreacted monomer or catalyst residue. The polymer network was further purified by Soxhlet extraction with acetone for 48 h. The product was dried in vacuo at 60 ° C for 24 h and ground to a fine black powder. A control sample (sulfur-containing conjugated microporous polymer (MP-S, non-graphite based)) was synthesized by the same procedure without RGBr.
將如此製成之含硫石墨基二維共軛微孔聚合物(GMP-S)在800℃下於氬氣氛圍下熱解2h，得到含硫石墨基二維中孔碳(指示為GMC-S)。藉由相同程序自含硫共軛微孔聚合物(MP-S)製備對照樣品含硫中孔碳(MC-S)。 The thus prepared sulfur-containing graphite-based two-dimensional conjugated microporous polymer (GMP-S) was pyrolyzed at 800 ° C for 2 h under an argon atmosphere to obtain a sulfur-containing graphite-based two-dimensional mesoporous carbon (indicated as GMC- S). A control sample containing sulfur mesoporous carbon (MC-S) was prepared from the sulfur-containing conjugated microporous polymer (MP-S) by the same procedure.
圖1顯示石墨基二維共軛微孔聚合物(GMP)及石墨基二維中孔碳(GMC)之製備(流程1)。 Figure 1 shows the preparation of a graphite-based two-dimensional conjugated microporous polymer (GMP) and graphite-based two-dimensional mesoporous carbon (GMC) (Scheme 1).
實施例2.本發明之二維石墨基共軛多孔聚合物及二維石墨基多孔碳與對應對照樣品之比較 Example 2. Comparison of two-dimensional graphite-based conjugated porous polymer and two-dimensional graphite-based porous carbon of the present invention with corresponding control samples
根據微孔粒度分佈比較實施例2中製備的本發明之二維石墨基共軛多孔聚合物及二維石墨基多孔碳與對應對照樣品。 The two-dimensional graphite-based conjugated porous polymer of the present invention and the two-dimensional graphite-based porous carbon prepared in Example 2 were compared with the corresponding control samples according to the pore size distribution.
GMP-S及MP-S之微孔粒度分佈呈現於圖2中。可見MP-S 及GMP-S二者之孔寬度均小於2nm。GMP-S顯示比MP-S少之大於2nm之孔。 The pore size distribution of GMP-S and MP-S is shown in Figure 2. Visible MP-S Both the GMP-S pore widths are less than 2 nm. GMP-S shows fewer pores larger than 2 nm than MP-S.
實施例3.希夫鹼型二維石墨基多孔聚合物及相關的二維石墨基多孔碳之製備，及其對照樣品之製備 Example 3. Preparation of Schiff base type two-dimensional graphite-based porous polymer and related two-dimensional graphite-based porous carbon, and preparation of its control sample
製備A. Preparation A.
在裝配有冷凝器及磁力攪拌棒之施蘭克燒瓶(Schlenk flask)中，將胺基官能化石墨烯氧化物(AGO，1當量，重量)分散於無水二甲亞碸中以形成溶液且接著將三聚氰胺及間苯二醛(4當量，莫耳比為2：3)添加至溶液中。在Ar鼓泡至少2小時之後，在惰性氛圍下將裝配有冷凝器及磁力攪拌棒之施蘭克燒瓶加熱至180℃持續72h。在冷卻至室溫之前，藉由快速過濾分離沈澱物且接著用過量DMF及丙酮洗滌，接著使用四氫呋喃進行索氏萃取3日。在室溫下於真空中移除溶劑以獲得具有良好產率(79%)的疏鬆粉末狀希夫鹼型二維石墨基多孔聚合物-1(TPP-1)(20%)。 Amine-functionalized graphene oxide (AGO, 1 equivalent, by weight) was dispersed in anhydrous dimethyl hydrazine to form a solution in a Schlenk flask equipped with a condenser and a magnetic stir bar to form a solution and then Melamine and isophthalaldehyde (4 equivalents, molar ratio of 2:3) were added to the solution. After bubbling Ar for at least 2 hours, the Schlenk flask equipped with a condenser and a magnetic stir bar was heated to 180 ° C for 72 h under an inert atmosphere. The precipitate was separated by rapid filtration and then washed with excess DMF and acetone before cooling to room temperature, followed by Soxhlet extraction using tetrahydrofuran for 3 days. The solvent was removed in vacuo at room temperature to obtain a loose powdery Schiff base type two-dimensional graphite-based porous polymer-1 (TPP-1) (20%) with good yield (79%).
將TPP-1置放於石英舟中且在氬氣流動下於5℃ min-1之加熱速率下加熱至800℃。將樣品保持於該溫度下2h。在冷卻至室溫之後，回收黑色粉末二維石墨基多孔碳-1(TPC-1)。 The TPP-1 was placed in a quartz boat and heated to 800 ° C under a argon flow at a heating rate of 5 ° C min -1 . The sample was kept at this temperature for 2 h. After cooling to room temperature, the black powder two-dimensional graphite-based porous carbon-1 (TPC-1) was recovered.
關於對照實驗，藉由相同程序製備無AGO模板之裸多孔聚合物(PP)。將製備之裸多孔聚合物置放於石英舟中且在氬氣流動下於5℃min-1之加熱速率下加熱至800℃。將樣品保持於該溫度下2h。在冷卻至室溫之後，回收黑色粉末狀二維多孔碳(PC)。 For the control experiment, a bare porous polymer (PP) without an AGO template was prepared by the same procedure. The prepared bare porous polymer was placed in a quartz boat and heated to 800 ° C under a flow of argon at a heating rate of 5 ° C min -1 . The sample was kept at this temperature for 2 h. After cooling to room temperature, black powdery two-dimensional porous carbon (PC) was recovered.
製備B. Preparation B.
1.胺化石墨烯氧化物(AGO)之製備：根據經改質Hummer's法自片狀石墨合成石墨烯氧化物。典型地，將石墨粉末(5.0g)添加至98% H2SO4(150mL)及NaNO3(3.75g)之混合物中。在於室溫下攪拌30分鐘之後，在1小時內分批添加KMnO4(20g)，且再攪拌20小時。五天後，添加去離子水(500mL)且接著緩慢添加H2O2(30mL)。將去離子水用於洗滌酸、金屬離子及未反應之石墨殘餘物若干次。在6000rpm下離心10分鐘之後，收集上部淡黃色溶液且冷凍乾燥。隨後將如此乾燥的石墨烯氧化物(1.0g)添加至無水DMF(250mL)中且經音波處理24h，隨後在0℃下將N-羥基琥珀醯亞胺(NHS，3.4g)及N-(3-(二甲胺基)丙基)-N-乙基碳化二亞胺鹽酸鹽(EDC．HCl，5.7g)添加至溶液中。在於0℃下攪拌2h之後，添加1,3-二胺基丙烷(2mL)，且將溶液在室溫下攪拌10h。在去離子水及乙醇洗滌且接著在40℃下真空乾燥隔夜之後，得到黑色粉末狀胺化石墨烯氧化物(AGO)。 1. Preparation of aminated graphene oxide (AGO): Synthesis of graphene oxide from flake graphite according to the modified Hummer's method. Typically, (5.0 g) was added to a mixture of 98% H 2 SO 4 (150mL ) and NaNO 3 (3.75g) of the graphite powder. After stirring at room temperature for 30 minutes, KMnO 4 (20 g) was added portionwise over 1 hour and stirred for additional 20 hours. Five days later, deionized water (500 mL) was slowly added and then H 2 O 2 (30mL). Deionized water was used to wash the acid, metal ions and unreacted graphite residue several times. After centrifugation at 6000 rpm for 10 minutes, the upper pale yellow solution was collected and lyophilized. The thus dried graphene oxide (1.0 g) was then added to anhydrous DMF (250 mL) and sonicated for 24 h, then N -hydroxysuccinimide (NHS, 3.4 g) and N- ( 3-(Dimethylamino)propyl) -N -ethylcarbodiimide hydrochloride (EDC.HCl, 5.7 g) was added to the solution. After stirring at 0 °C for 2 h, 1,3-diaminopropane (2 mL) was added and the solution was stirred at room temperature for 10 h. After washing with deionized water and ethanol and then vacuum drying at 40 ° C overnight, a black powdery aminated graphene oxide (AGO) was obtained.
2.希夫鹼型二維石墨基多孔聚合物-1(TPP-1)(5%)、TPP-1(10%)及TPP-1(20%)之合成：在裝配有冷凝器及磁力攪拌棒之施蘭克燒瓶中，將胺化石墨烯氧化物(AGO)(1當量，重量)充分分散於無水二甲亞碸(DMSO)中且接著將三聚氰胺及間苯二醛(分別為19當量、9當量及4當量，莫耳比為2：3)添加至溶液中。在氮氣鼓泡至少2小時之後，在惰性氛圍下將裝配有冷凝器及磁力攪拌棒之施蘭克燒瓶加熱至180℃持續72h。在冷卻至室溫之前，藉由快速過濾分離沈澱物以移除並非靜置於石墨烯表面上之 自由粒子且接著用過量DMF及丙酮洗滌且接著使用THF進行索氏分餾3日。在室溫下於真空中移除溶劑，獲得具有良好產率(70%-90%)的疏鬆粉末狀材料。 2. Synthesis of Schiff base type two-dimensional graphite-based porous polymer-1 (TPP-1) (5%), TPP-1 (10%) and TPP-1 (20%): equipped with condenser and magnetic force Aminating graphene oxide (AGO) (1 equivalent, by weight) was thoroughly dispersed in anhydrous dimethyl hydrazine (DMSO) and then melamine and isophthalaldehyde (19, respectively) in a stir bar flask Equivalent, 9 equivalents and 4 equivalents, molar ratio of 2:3) were added to the solution. After bubbling nitrogen for at least 2 hours, the Schlenk flask equipped with a condenser and a magnetic stir bar was heated to 180 ° C for 72 h under an inert atmosphere. The precipitate was separated by rapid filtration to remove the non-statically placed on the surface of the graphene before cooling to room temperature. The free particles were then washed with excess DMF and acetone and then subjected to Soxhlet fractionation for 3 days using THF. The solvent was removed in vacuo at room temperature to give a loose powdery material with good yield (70% to 90%).
3. TPP-1(5%)、TPP-1(10%)及TPP-1(20%)之熱解：將200mg TPP-1(5%)置放於石英舟中且在氬氣流動下於5℃/min之加熱速率下加熱至X℃(X=700、800及900)。將樣品保持於該溫度下2h。在冷卻至室溫之後，回收黑色粉末TPC-1(5%)-X℃。對於具有不同石墨烯含量之樣品二維石墨基多孔碳-1(TPC-1)(10%)及TPC-1(20%)，亦使用相同程序獲得熱解產物TPC-1(10%)-X℃及TPC-1(20%)-X℃。 3. Pyrolysis of TPP-1 (5%), TPP-1 (10%) and TPP-1 (20%): 200 mg TPP-1 (5%) was placed in a quartz boat under argon flow Heat to X ° C (X = 700, 800 and 900) at a heating rate of 5 ° C / min. The sample was kept at this temperature for 2 h. After cooling to room temperature, the black powder TPC-1 (5%) - X ° C was recovered. For samples with different graphene contents, two-dimensional graphite-based porous carbon-1 (TPC-1) (10%) and TPC-1 (20%), the same procedure was used to obtain the pyrolysis product TPC-1 (10%)- X ° C and TPC-1 (20%) - X ° C.
在圖3中顯示希夫鹼型二維石墨基多孔聚合物之合成(流程2)。 The synthesis of a Schiff base type two-dimensional graphite-based porous polymer is shown in Fig. 3 (Scheme 2).
實施例4.石墨基二維多孔聚合物及石墨基二維多孔碳與非石墨基二維多孔聚合物及二維多孔碳之形態之比較 Example 4. Comparison of Graphite-based Two-Dimensional Porous Polymer and Graphite-Based Two-Dimensional Porous Carbon and Non-Graphite-Based Two-Dimensional Porous Polymer and Two-Dimensional Porous Carbon
圖4顯示石墨基二維共軛微孔聚合物之影像，其中(a)為含硫石墨基二維共軛微孔聚合物(GMP-S)之SEM影像，(b)為GMP-S之AFM影像，(c)為GMP-S之TEM影像，且(d)為含硫共軛微孔聚合物(MP-S)之SEM影像。 Figure 4 shows an image of a graphite-based two-dimensional conjugated microporous polymer, wherein (a) is a SEM image of a sulfur-containing graphite-based two-dimensional conjugated microporous polymer (GMP-S), and (b) is a GMP-S AFM image, (c) is a TEM image of GMP-S, and (d) is an SEM image of a sulfur-containing conjugated microporous polymer (MP-S).
所有GMP顯示類似薄片形態。因此，在本文中將GMP-S之結果論述為典型實施例。如圖4中所示，觀測到多種形態類似於石墨烯且尺寸在200nm至幾微米範圍內之獨立式薄片。另外，此等多孔聚合物薄片展示皺折及可撓性特徵。在TEM或SEM觀測中未出現自由多孔聚合物 粒子或裸石墨烯薄片。此表明正如預期的，大部分單體已聚合於石墨烯表面上。典型AFM及厚度分析(圖4之圖b))顯示與藉由SEM及TEM所觀測到之相同的形態，具有40±3nm之均一厚度。無石墨烯模板之對照樣品MP-S展示如先前技術中所報導之常見非結晶奈米顆粒結構(圖4之圖d))。此等結果強有力地表明石墨烯作為基板用於在2D方式內接枝共軛微孔聚合物之關鍵作用。 All GMPs showed a similar flake morphology. Therefore, the results of GMP-S are discussed herein as exemplary embodiments. As shown in FIG. 4, a plurality of free-standing sheets having a morphology similar to graphene and having a size ranging from 200 nm to several micrometers were observed. Additionally, such porous polymer sheets exhibit wrinkle and flexibility characteristics. Free porous polymer did not appear in TEM or SEM observations Particle or bare graphene sheets. This indicates that as expected, most of the monomers have been polymerized on the graphene surface. A typical AFM and thickness analysis (Fig. 4, panel b)) shows the same morphology as observed by SEM and TEM, with a uniform thickness of 40 ± 3 nm. The control sample MP-S without the graphene template exhibited the common amorphous nanoparticle structure as reported in the prior art (Fig. 4, panel d)). These results strongly suggest that graphene acts as a substrate for the critical role of grafting conjugated microporous polymers in a 2D manner.
實施例5.電化學效能之比較 Example 5. Comparison of electrochemical performance
典型地檢測含硫石墨基二維中孔碳(GMC-S)及含硫中孔碳(MC-S)之超級電容器特性且將結果顯示於圖5中。圖5顯示在6M KOH溶液中於10mV s-1下的MC-S及GMC-S之CV曲線(左側)及在0.1Ag-1之電流密度下的MC-S及GMC-S之恆電流充電/放電曲線(右側)。 Supercapacitor characteristics of sulfur-containing graphite-based two-dimensional mesoporous carbon (GMC-S) and sulfur-containing mesoporous carbon (MC-S) are typically measured and the results are shown in FIG. Figure 5 shows the CV curves of MC-S and GMC-S at 10 mV s -1 in 6 M KOH solution (left side) and constant current charging of MC-S and GMC-S at a current density of 0.1 Ag -1 / discharge curve (right side).
如圖5(左側)中所示，對於MC-S及GMC-S二者觀測到對稱及水平CV曲線，表明理想電容特性。對於GMC-S觀測到顯著高於MC-S之電流密度，其表明石墨烯層有助於增加電容。藉由恆電流充電/放電循環實驗(圖5，右側)進一步研究電容效能。基於放電曲線，在0.1Ag-1下之GMC-S之比電容經計算為268Fg-1，其比MC-S之比電容(235Fg-1)高12%。在此超級電容器應用中，由於高導電性及二維共軛特徵，夾心型GMC中之石墨烯層可在催化及充電/放電過程期間充當微型集電器及長距離平面內電荷輸送體二者。 As shown in Figure 5 (left side), symmetrical and horizontal CV curves were observed for both MC-S and GMC-S, indicating ideal capacitance characteristics. A significant higher current density than MC-S was observed for GMC-S, indicating that the graphene layer contributes to increased capacitance. Capacitance performance was further investigated by a constant current charge/discharge cycle experiment (Fig. 5, right side). Based on the discharge curve, the specific capacitance of GMC-S at 0.1 Ag -1 was calculated to be 268 Fg -1 , which is 12% higher than the specific capacitance of MC-S (235 Fg -1 ). In this supercapacitor application, the graphene layer in the sandwich type GMC can function as both a microcollector and a long-distance in-plane charge transport during the catalytic and charging/discharging processes due to the high conductivity and two-dimensional conjugate characteristics.
實施例6.超級電容器效能之比較 Example 6. Comparison of supercapacitor performance
在圖6中顯示關於超級電容器效能之比較。 A comparison of the performance of the supercapacitor is shown in FIG.
比較藉由相同條件在無石墨烯模板之情況下自裸多孔聚合 物製備之二維石墨基多孔碳(TPC)及二維多孔碳(PC)之超級電容器效能。 Comparison of bare porous polymerization by the same conditions without graphene template Two-dimensional graphite-based porous carbon (TPC) and two-dimensional porous carbon (PC) supercapacitor performance.
圖6之圖a)顯示在6M KOH水溶液中於5mV s-1下的PC及TPC之CV曲線。 Figure 6 is a graph showing the CV curves of PC and TPC at 5 mV s -1 in 6 M aqueous KOH solution.
圖6之圖b)顯示在0.1Ag-1之電流密度下的PC及TPC之恆電流充電/放電曲線。 Figure b) shows a constant current charge/discharge curve for PC and TPC at a current density of 0.1 Ag -1 .
圖6之圖c)顯示在開路電壓下的PC及TPC之奈奎斯曲線(Nyquist plot)。插圖顯示曲線之擴展的高頻區域。 Figure 6 Figure c) shows the Nyquist plot of PC and TPC at open circuit voltage. The illustration shows the extended high frequency area of the curve.
圖6之圖d)顯示TPC薄片中之電子之儲存及釋放，其中石墨烯在充電及放電過程期間充當微型集電器及平面內導體。將熱解溫度800℃用於製備此等樣品。 Figure d, Figure d) shows the storage and release of electrons in a TPC sheet, wherein graphene acts as a micro current collector and an in-plane conductor during the charging and discharging process. A pyrolysis temperature of 800 ° C was used to prepare these samples.
所有電容測試下之二維石墨基多孔碳(TPC)均為800℃下的對應希夫鹼型二維石墨基多孔聚合物之熱解產物。如圖6之圖a)中之循環伏安法(CV)曲線中所示，對於PC及TPC膜二者觀測到對稱及水平CV曲線，表明理想電容特性。藉由恆電流充電/放電循環實驗(圖6之圖b))進一步研究電容效能。在0.1Ag-1下的TPC之比電容經計算為424Fg-1，其幾乎比PC之比電容(354Fg-1)高20%。可在PC中觀測到反映電極碳材料之不佳導電性及較大電阻的顯著內電阻(IR)下降。相比之下，在TPC中幾乎不可偵測到IR下降。圖6之圖c)中呈現的PC及TPC之阻抗譜亦展示此種狀況。TPC之較小半圓指示較小電荷轉移電阻。根據等效電路，關於TPC及PC所計算之電荷轉移電阻分別為0.17Ω及0.69Ω。等效串聯電阻(ESR)之降低在增加超級電容器之特定功率輸出中為關鍵 的。如圖6之圖d)所說明，由於熱還原及二維共軛特徵，此種類之夾心型TPP中之石墨烯層可在充電及放電過程期間充當微型集電器及長距離平面內電荷輸送體二者。 The two-dimensional graphite-based porous carbon (TPC) under all capacitance tests is a pyrolysis product of a corresponding Schiff base type two-dimensional graphite-based porous polymer at 800 °C. As shown in the cyclic voltammetry (CV) curve in panel a) of Figure 6, symmetrical and horizontal CV curves were observed for both PC and TPC films, indicating ideal capacitance characteristics. Capacitance performance was further investigated by a constant current charge/discharge cycle experiment (Fig. 6 panel b). The specific capacitance of TPC at 0.1 Ag -1 is calculated to be 424 Fg -1 , which is almost 20% higher than the specific capacitance of PC (354Fg -1 ). A significant internal resistance (IR) drop reflecting the poor conductivity of the electrode carbon material and the large resistance can be observed in the PC. In contrast, almost no IR drop can be detected in TPC. The impedance spectra of PC and TPC presented in Figure c) of Figure 6 also show this situation. The smaller semicircle of the TPC indicates a smaller charge transfer resistance. According to the equivalent circuit, the charge transfer resistance calculated for TPC and PC is 0.17 Ω and 0.69 Ω, respectively. The reduction in equivalent series resistance (ESR) is critical in increasing the specific power output of a supercapacitor. As illustrated in Figure d), due to thermal reduction and two-dimensional conjugate characteristics, the graphene layer in this type of sandwich TPP can act as a micro-collector and a long-distance in-plane charge transport during charging and discharging processes. both.
實施例7.聚合物網狀物之共軛性質之效果的比較 Example 7. Comparison of the effects of conjugate properties of polymer networks
圖7顯示在550-600nm下監測到的含硫共軛微孔聚合物(MP-S)及含硫石墨基二維共軛微孔聚合物(GMP-S)之螢光衰減及對應的伸展指數擬合(λex=400nm)。 Figure 7 shows the fluorescence decay and corresponding stretching of sulfur-containing conjugated microporous polymer (MP-S) and sulfur-containing graphite-based two-dimensional conjugated microporous polymer (GMP-S) monitored at 550-600 nm. Exponential fit (λ ex =400 nm).
鑒於聚合物網狀物之共軛性質，藉由時差式光致發光光譜特性進一步研究GMP-S及MP-S之激子動力學。如圖7中所示，MP-S展現伸展指數衰減，其表明壽命分佈。衰減可與5.19ps之逆速率常數及0.34之拉伸指數擬合。發現拉伸指數(β=0.31)類似於GMP-S，而衰減顯著較快，逆速率常數為1.76ps。此結果意味著在GMP-S中之石墨烯薄片與多孔聚合物網狀物之間存在電子相互作用，GMP-S之性質為進一步調查之主題。然而，看起來石墨烯薄片充當電子受體，而共軛微孔聚合物殼層充當電子供體。使用石墨烯薄片作為超薄電子接受層之該夾心樣D-A-D型多孔有機材料可為某些電子應用帶來希望。 In view of the conjugated nature of the polymer network, the exciton kinetics of GMP-S and MP-S were further investigated by time-lapse photoluminescence spectroscopy. As shown in Figure 7, MP-S exhibits a stretch index decay, which indicates a life distribution. The attenuation can be fitted to an inverse rate constant of 5.19 ps and a tensile index of 0.34. The tensile index (β = 0.31) was found to be similar to GMP-S, while the attenuation was significantly faster and the inverse rate constant was 1.76 ps. This result means that there is an electronic interaction between the graphene flakes in the GMP-S and the porous polymer network, and the nature of GMP-S is the subject of further investigation. However, it appears that the graphene sheets act as electron acceptors, while the conjugated microporous polymer shell acts as an electron donor. The sandwich-like D-A-D type porous organic material using graphene sheets as an ultra-thin electron-receiving layer can bring hope to certain electronic applications.
實施例8.石墨基二維多孔碳中摻雜之雜原子之效果的比較 Example 8. Comparison of the effects of doping heteroatoms in graphite-based two-dimensional porous carbon
藉由在氬氣氛圍下於800℃下直接熱解GMP持續2h產生含硫石墨基二維中孔碳(GMC-S)、含氮及含硫石墨基二維中孔碳(GMC-NS)及含氮石墨基二維中孔碳(GMC-N)，分別表示為GMC-S、GMC-NS及GMC-N。為進行比較，亦藉助於相同程序但在不包含石墨烯模板之情況下自含硫共軛微孔聚合物(MP)製備中孔碳，且分別表示為MC-S、MC- NS及MC-N。GMC-S及GMC-NS中之硫的重量含量分別為7.7%及5.9%，且GMC-NS及GMC-N中之氮比分別達到3.0%及3.8%。 Two-dimensional mesoporous carbon (GMC-S), nitrogen-containing and sulfur-containing graphite-based two-dimensional mesoporous carbon (GMC-NS) produced by direct pyrolysis of GMP at 800 ° C for 2 h under argon atmosphere And nitrogen-containing graphite-based two-dimensional mesoporous carbon (GMC-N), which are represented as GMC-S, GMC-NS and GMC-N, respectively. For comparison, mesoporous carbon was also prepared from sulfur-containing conjugated microporous polymer (MP) by the same procedure but without the inclusion of a graphene template, and was expressed as MC-S, MC-, respectively. NS and MC-N. The weight contents of sulfur in GMC-S and GMC-NS were 7.7% and 5.9%, respectively, and the nitrogen ratios in GMC-NS and GMC-N were 3.0% and 3.8%, respectively.
此策略因此實現建構具有高雜原子摻雜含量之二維多孔碳的可行方式。 This strategy thus enables a viable way to construct a two-dimensional porous carbon with a high heteroatom doping content.
實施例9.其他效能 Example 9. Other performance
共軛微孔聚合物為富含碳之前驅體類型，其可將雜原子、金屬及金屬氧化物整合至碳架中以用於各種應用，諸如能量儲存及電化學催化。熱解重量分析(TGA)顯示MP及GMP二者均可以高碳產率(70%-90%)可行地轉化成碳材料。因此，藉由在氬氣氛圍下於800℃下直接熱解GMP持續2h產生S-、N/S-及N-摻雜之二維多孔碳，分別表示為GMC-S、GMC-NS及GMC-N。應注意GMC-S、GMC-NS及GMC-N維持具有較大縱橫比之二維形態以及分別具有618、681及560m2 g-1之高BET表面積之多孔特徵。為進行比較，亦藉助於相同程序但在不包含石墨烯模板之情況下自MP製備多孔碳，且分別表示為MC-S、MC-NS及MC-N：其表面積在554-636m2 g-1範圍內。相對於對應GMP及MP的GMC及MC之表面積減小可能係由於在碳化條件下之聚合物降解及片段重組。 Conjugated microporous polymers are carbon-rich precursor types that integrate heteroatoms, metals, and metal oxides into carbon holders for a variety of applications, such as energy storage and electrochemical catalysis. Thermogravimetric analysis (TGA) shows that both MP and GMP can be converted to carbon materials in a high carbon yield (70%-90%). Therefore, S-, N/S- and N-doped two-dimensional porous carbons are produced by direct pyrolysis of GMP at 800 ° C for 2 h under argon atmosphere, denoted as GMC-S, GMC-NS and GMC, respectively. -N. It should be noted that GMC-S, GMC-NS and GMC-N maintain a two-dimensional morphology with a large aspect ratio and a porous feature with a high BET surface area of 618, 681 and 560 m 2 g -1 , respectively. For comparison, porous carbon was also prepared from MP by means of the same procedure but without the inclusion of a graphene template, and was denoted as MC-S, MC-NS and MC-N, respectively, with a surface area of 554-636 m 2 g - 1 range. The decrease in surface area relative to GMC and MC corresponding to GMP and MP may be due to polymer degradation and fragment recombination under carbonization conditions.
其他電化學效能顯示於表1中。 Other electrochemical performances are shown in Table 1.
對於希夫鹼型多孔聚合物：TEM影像中之交替暗明資訊表明此材料中存在許多孔，然而，由於劇烈分解，並非所有孔及通道可在熱解之後維持。藉由氮氣物理吸附量測進一步確認碳薄片之多孔性質。孔徑分佈曲線指示存在中孔且在約2.6nm之孔直徑處具有最大峰值。對於分別在700、800及900℃下之熱解仍展現高達399、364及323m2g-1之比表面積。在惰性氛圍下分別於700℃、800℃及900℃下碳化時，氮含量自熱解之前的25.6%減小至12.7%、10.0%及7.8%。 For Schiff base type porous polymers: alternating darkening information in TEM images indicates that there are many pores in this material, however, due to violent decomposition, not all pores and channels can be maintained after pyrolysis. The porous nature of the carbon flakes was further confirmed by nitrogen sorption measurement. The pore size distribution curve indicates the presence of a mesopores and has a maximum peak at a pore diameter of about 2.6 nm. The pyrolysis at 700, 800 and 900 ° C respectively still exhibits a specific surface area of up to 399, 364 and 323 m 2 g -1 . When carbonized at 700 ° C, 800 ° C and 900 ° C under an inert atmosphere, the nitrogen content decreased from 25.6% before pyrolysis to 12.7%, 10.0% and 7.8%.
上文提及之文獻中之每一者係以引用之方式併入本文中。 Each of the above mentioned documents is incorporated herein by reference.
除在實施例中，或另外明確指示外，在本說明書中規定材料之量、反應條件及其類似者之所有數值量均理解為藉由字語「約」修飾。 In the examples, or in addition to the explicit indications, all quantities of the quantities of the materials, the reaction conditions, and the like in the specification are understood to be modified by the word "about".
應理解，可獨立地合併本文中闡述的量、範圍及比之上限及下限。類似地，本發明之各要素之範圍及量可與其他要素中之任一者之 範圍或量一起使用。 It should be understood that the amounts, ranges, and ratios of the upper and lower limits set forth herein may be combined independently. Similarly, the scope and quantity of each element of the invention may be combined with any of the other elements. The range or amount is used together.
本發明不受本文所述之特定具體實例及實施例限制範疇。實際上，根據前述描述及隨附圖式，除了本文中所述之修改之外，本發明之各種修改對熟習此項技術者而言亦將變得顯而易見。該等修改意欲在隨附申請專利範圍之範疇內。 The present invention is not to be limited by the specific examples and embodiments described herein. In fact, various modifications of the invention in addition to those described herein will become apparent to those skilled in the art. Such modifications are intended to be within the scope of the accompanying claims.
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