Two‐Dimensional Sandwich‐Type, Graphene‐Based Conjugated Microporous Polymers

Abstract

Porous polymers [1] with porosity at the nanoscale have attracted tremendous attention since their porous features are associated with prominent physical properties and since they have potential applications in, for example, light harvesting, [2] sensing, [3] gas separation [4] and storage, [5] catalysis, [6] and energy storage and conversion. [7] There are several classes of micro-/mesoporous polymers, such as hyper-crosslinked polymers (HCPs), polymers of intrinsic microporosity (PIMs), and covalent organic frameworks (COFs). Porous polymers can be also classified according to their structural conformations as amorphous-(HCPs and PIMs) or crystalline-type (COFs) materials. [1e] Conjugated microporous polymers (CMPs) represent one of the fastest developing types of porous materials not only because of their efficient synthesis by conventional metal-catalyzed polymerization techniques and the availability of a large number of commercially available functional monomers but also due to their controllable and adaptable physical properties. [1d] Unlike COFs, CMPs are formed under kinetic control, and thus are amorphous and show no longrange structural order. [8] For this reason, most of the previous work on CMPs has been focused on developing new chemical strategies and tuning the pore size distribution and surface area of these polymers by varying the length of the organic linkers rather than through morphology control. Very recently, efforts have been made to synthesize CMPs with controlled nanostructures, such as quasi-zero-dimensional microspheres, [9] and one-dimensional nanofibers [10] and nanotubes [11] as well as three-dimensional monoliths. [12] However, the synthesis of porous polymers with two-dimensional (2D) sheet structures remains little explored. Dichtel et al. employed a solvothermal method to grow oriented 2D COF thin films on substrate-supported graphene by the dynamic assembly of boronic acid and hexahydroxytriphenylene monomers, [13] but the large-scale production of free-standing 2D porous polymer networks has not yet been achieved.Graphene, because of its single-atom thickness, large aspect ratio, high surface area, and many intriguing physical properties, has proved to be a promising template for the highly efficient construction of 2D porous nanohybrid materials, such as 2D porous silica, [14] metal oxides, [15] metal sulfides, [16] carbon nitride, [17] and carbon-coated graphene/ metal oxide sheets. [18] All these approaches typically rely on the use of a graphene-based porous silica template in nanocasting technology or the nucleation of metal oxide or sulfide nanostructures on the graphene surface. Nevertheless, the porous structures of these graphene-based hybrid materials cannot be tailored at the molecular level, as has been done for organic porous materials. [1] We report herein on a graphene-inspired synthetic approach to the large-scale production of 2D sandwichlike conjugated microporous polymers in which each graphene sheet is fully separated by a porous polymer shell. Thiophene...

Compact Coupled Graphene and Porous Polyaryltriazine‐Derived Frameworks as High Performance Cathodes for Lithium‐Ion Batteries

“…

It is highly desirable to develop electroactive organic materials and their derivatives as green alternatives of cathodes for sustainable and cost-effective lithium-ion batteries (LIBs) in energy storage fields. Therefore, there is an urgent demand for designing and constructing cathodes with a high energy density and long cycle life for the nextgeneration LIBs.The judiciously designed two-dimensional (2D) graphenebased porous nanohybrids possess large aspect ratios, welldefined pore structures, high surface areas, and excellent electrical conductivity, [5] which demonstrate appeal as electrode materials in LIBs. The porous nanosheets display nanoscale thickness, high specific surface area, and strong coupling of electroactive polyaryltriazine-derived frameworks with graphene.

…”

Progress of Nanostructured Electrode Materials for Supercapacitors

“…Zhuang et al reported a graphene-inspired synthetic approach to large-scale preparation of 2D conjugated microporous polymers (CMPs), and then, the heteroatom-doped 2D porous carbon was generated by the direct pyrolysis of GMPs under an argon atmosphere. [77] By using the metal-catalyzed Sonogashira-Hagihara coupling reaction, the thiophene-, thiazole-, and pyridine-based monomers can be polymerized with 1,3,5-triethynylbenzene monomer on the graphene surface (Figure 11a). In their research, this polymer nanosheets exhibited large aspect radios, high surface areas, and hierarchical porous structure, thus the direct carbonized carbon still maintained a 2D morphology (Figure 11b).…”

“…[77] Copyright 2013, Wiley-VCH. d) Preparation schematic diagram of GHCPs, e,f) TEM images of GHCP-1-900.…”

Photoelectronic Porous Covalent Organic Materials: Research Progress and Perspective

“…[104] . 14a : (GO) , GO, Sonogashira-Hagihara : C M P (Graphene-based conjugated microporous polymer sheets: GMPs).…”

“…(d) Schematic representation of the chemical synthesis of metalloporphyrin-based conjugated mesoporous polymer frameworks (M Co, H 2 ) (e) LSV curves for CoP-CMP, CoP-CMP600, CoP-CMP800, CoP-CMP1000, H2P-CMP800, and Pt/C in O 2 -saturated 0.1 mol/L KOH. (f) The n values of CoP-CMP, CoP-CMP600, CoP-CMP800, CoP-CMP1000, H 2 P-CMP800, and Pt/C against electrode potential [103] 14 (a) COM (GMPs) (GMCs) [104] .…”