Porous graphenes: two-dimensional polymer synthesis with atomic precision

Bieri, Marco; Treier, Matthias; Cai, Jinming; Aït-Mansour, Kamel; Ruffieux, Pascal; Gröning, Oliver; Gröning, P.; Kastler, Marcel; Rieger, Ralph; Feng, Xinliang; Müllen, Kläus; Fasel, Román

doi:10.1039/b915190g

Cited by 635 publications

(552 citation statements)

References 26 publications

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“…From these measurements, we confirmed the formation of a short-range-ordered 2D polymeric framework constituted by aromatic rings. Therefore, the BPOE shows adjustable electronic properties and controllable semiconducting features emerging from their structural periodicity comparable to 2D atomic crystals, such as multilayer graphene, and a choice of monomer as a building block [39][40][41][42][43][44][45] . Here we demonstrate that the bipolar characters of the BPOE required for high-performance electrochemical properties are preserved even in a sodium battery system.…”

Section: Resultsmentioning

confidence: 99%

Aromatic porous-honeycomb electrodes for a sodium-organic energy storage device

et al. 2013

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Rechargeable batteries using organic electrodes and sodium as a charge carrier can be highperformance, affordable energy storage devices due to the abundance of both sodium and organic materials. However, only few organic materials have been found to be active in sodium battery systems. Here we report a high-performance sodium-based energy storage device using a bipolar porous organic electrode constituted of aromatic rings in a porous-honeycomb structure. Unlike typical organic electrodes in sodium battery systems, the bipolar porous organic electrode has a high specific power of 10 kW kg À 1 , specific energy of 500 Wh kg À 1 , and over 7,000 cycle life retaining 80% of its initial capacity in half-cells. The use of bipolar porous organic electrode in a sodium-organic energy storage device would significantly enhance cost-effectiveness, and reduce the dependency on limited natural resources. The present findings suggest that bipolar porous organic electrode provides a new material platform for the development of a rechargeable energy storage technology.

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Section: Resultsmentioning

confidence: 99%

Aromatic porous-honeycomb electrodes for a sodium-organic energy storage device

et al. 2013

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“…The morphology of the resulting polyphenylene networks differs significantly: On Cu, the growth of dendritic network structures with single-molecule-wide branches prevails; the Au surface promotes the evolution of small 2D network domains, and on the Ag surface extended and well-ordered 2D networks emerge as we have reported recently. 25,26 With the aid of density functional theory (DFT) calculations, the nature of the surface-stabilized CHPRs, as well as the details of diffusion and reaction pathways, are elucidated. We find that on Cu, diffusion of CHPR is hindered, while the coupling step is significantly promoted.…”

Section: Introductionmentioning

confidence: 99%

Two-Dimensional Polymer Formation on Surfaces: Insight into the Roles of Precursor Mobility and Reactivity

et al. 2010

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Abstract:We report on a combined scanning tunneling microscopy (STM), X-ray photoelectron spectroscopy (XPS), and density functional theory (DFT) study on the surface-assisted assembly of the hexaiodosubstituted macrocycle cyclohexa-m-phenylene (CHP) toward covalently bonded polyphenylene networks on Cu(111), Au(111), and Ag(111) surfaces. STM and XPS indicate room temperature dehalogenation of CHP on either surface, leading to surface-stabilized CHP radicals (CHPRs) and coadsorbed iodine. Subsequent covalent intermolecular bond formation between CHPRs is thermally activated and is found to proceed at different temperatures on the three coinage metals. The resulting polyphenylene networks differ significantly in morphology on the three substrates: On Cu, the networks are dominated by "open" branched structures, on the Au surface a mixture of branched and small domains of compact network clusters are observed, and highly ordered and dense polyphenylene networks form on the Ag surface. Ab initio DFT calculations allow one to elucidate the diffusion and coupling mechanisms of CHPRs on the Cu(111) and Ag(111) surfaces. On Cu, the energy barrier for diffusion is significantly higher than the one for covalent intermolecular bond formation, whereas on Ag the reverse relation holds. By using a Monte Carlo simulation, we show that different balances between diffusion and intermolecular coupling determine the observed branched and compact polyphenylene networks on the Cu and Ag surface, respectively, demonstrating that the choice of the substrate plays a crucial role in the formation of two-dimensional polymers.

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“…12 Recent examples of this are the formation of graphene nanoribbons and porous graphene on metal substrates. [13][14][15] The synthesis of porous graphene is based on the molecular precursor 5,5′,5′′,5′′′,5′′′′,5′′′′′-hexaiodo-cyclohexa-mphenylene (I 6 -CHP, cf. inset in Fig.…”

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confidence: 99%

Dehalogenation and Coupling of a Polycyclic Hydrocarbon on an Atomically Thin Insulator

et al. 2014

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Catalytic activity is of pivotal relevance in enabling efficient and selective synthesis processes.Recently, covalent coupling reactions catalyzed by solid metal surfaces opened the rapidly evolving field of on-surface chemical synthesis. Tailored molecular precursors in conjunction with the catalytic activity of the metal substrate allow the synthesis of novel, technologically highly relevant materials such as atomically precise graphene nanoribbons. However, the reaction path on the metal substrate remains unclear in most cases and the intriguing question is how a specific atomic configuration between reactant and catalyst controls the reaction processes. In this study, we cover the metal substrate with a monolayer of hexagonal boron nitride (h-BN), reducing the reactivity of the metal, and gain unique access to atomistic details during the activation of a polyphenylene precursor by sequential dehalogenation and the subsequent coupling to extended oligomers. We use scanning tunneling microscopy (STM) and density functional theory (DFT) to reveal a reaction site anisotropy, induced by the registry mismatch between the precursor and the nano-structured h-BN monolayer. 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60 3 An atomically thin layer of insulating h-BN is a structurally analogous counterpart for graphene -a single layer of sp 2 -hybridised carbon atoms 1 -matching the graphene lattice almost perfectly with a small mismatch of approx. 2%. Currently, the fabrication of two-dimensional materials follows two main approaches: i) the bottom-up synthesis by substrate supported chemical vapor deposition (CVD) with suitable precursors and ii) the top-down approach by exfoliation. The assembly of graphene/h-BN heterostructures, leading to novel devices or devices with enhanced performance, usually relies on elaborate, sequential transfer processes of the produced layers. 2 The main obstacles are possible misalignment, introduction of defects and contaminations resulting from transferring layers that are just one atom thick. Only recently, the direct CVD growth of graphene on h-BN was demonstrated, offering superior properties. [3][4][5] However, the growth conditions are harsh (long exposure time, high temperatures, several cycles, etc.). Metal substrates are favored, because of their high catalytic activity, 6 but they have the disadvantage that they strongly alter the properties of the grown layers, which therefore cannot be directly used for electronic device fabrication.A common motif in on-surface chemical reactions is the activation of a precursor, the intermittent complex formed between precursor and substrate, and finally the coupling reaction. 7A long-standing question is the impact of the specific atomic configuration between substrate and reactant on the catalytic efficiency and how does the specific atomic arrangement chan...

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Porous graphenes: two-dimensional polymer synthesis with atomic precision

Abstract: We demonstrate, by surface-assisted coupling of specifically designed molecular building blocks, the fabrication of regular two-dimensional polyphenylene networks with single-atom wide pores and sub-nanometer periodicity.

Cited by 635 publications

References 26 publications

Aromatic porous-honeycomb electrodes for a sodium-organic energy storage device

Aromatic porous-honeycomb electrodes for a sodium-organic energy storage device

Two-Dimensional Polymer Formation on Surfaces: Insight into the Roles of Precursor Mobility and Reactivity

Dehalogenation and Coupling of a Polycyclic Hydrocarbon on an Atomically Thin Insulator

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