Nano Today
Volume 10, Issue 5, October 2015, Pages 593-614
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Review
Domino games: Controlling structure and patterns of carbon nanomaterials in 2D & 3D

https://doi.org/10.1016/j.nantod.2015.07.003Get rights and content

Highlights

  • Carbon is – from all materials – the materials with the smallest “voxel” size, i.e. finest possible details can be synthesized, replicated, or imprinted to promote nanoscience.

  • The construction of “patches” within carbon nanostructures expands the chemical functionality significantly.

  • This for instance results in improved conductivity, electrocatalytic activity, and stability.

  • Preorganization of monomers to be condensed towards carbon is necessary to access rational “patching”.

Summary

This perspective article reviews and conceptualizes some paths towards structured nanoobjects made of carbon. We focus on possibilities where controlled patterns within 2D carbon planes or in 3D volume objects are important as they are able to enhanced or even introduce new properties. For instance, one can pattern electron poor and electron rich domains of carbon, resulting in donor–acceptor based charge separation and transport. A novel chemistry towards such designer carbons, however, can only be made accessible if control over (high temperature) reactions can be introduced and improved, i.e. product geometry and properties have been determined throughout the condensation reaction as early as possible.

The task is to transcribe dynamic but at the same time very ordered monomers and monomer patterns into functional carbons, while keeping the targeted structure as much as possible. Here, precursors with “encoded information” and the utilization of (natural) assembly and bonding schemes such as strong H-bridges, polymeric character, Coulomb forces or metal coordination are promising tools and presented.

Graphical abstract

The article highlights a new trend in carbon nanomaterials, the control of functionality and patterns within the planes by polymer-like condensation of defined and prealigned building blocks.

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Section snippets

Functional molecules and additives

The preparation of carbons may sound easy as it seems to be a kind of “burning” action. However, the indeed tedious quest for suitable precursors and methods becomes clear rather fast. This is, besides others, not at least due to the still relatively unpredictable processes occurring at higher temperatures as well as the lack of char-forming materials: most molecules simply “vanish” in form of volatile fragments of high stability. And, as simple as it sounds: a high carbonization yield is

Polymers and larger starting molecules

Another way to avoid volatility and to end up with higher carbon yields and thereby potentially also higher structural preservation of precursor structures is the employment of stable larger molecules and polymers. This is why nowadays more and more also organic and polymer chemistry contribute to the field of carbon materials. Recently, Sakamoto and co-workers presented the synthesis of a periodic two-dimensional polymer network by organic synthesis reminiscent to graphene [21]. Here, the

Dynamic processes and in situ nanocoating

Wang and co-workers presented a nice example where the combination of an easily carbonizeable carbohydrate and the structured crystal of the functional comonomer underwent a controlled self-transformation process towards a structured nitrogen-doped carbon (Fig. 8) [28].

Here, micelles (used as soft templates) were co-assembled on the surface of melamine sulfate crystals, which during hydrothermal carbonization (HTC) of fructose (as a precursor with very high carbonization yield, following the

Liquid crystalline precursors

A most nearby way to pre-organize and assemble the precursor units is by using liquid crystallinity. Maybe slightly faded into obscurity, but one of the first high quality carbon fiber was spun from so-called “mesophase pitch”, a tar product constituted from larger aromatic discotic entities which self-assembled into liquid crystalline nematic phases at elevated temperatures [35]. In terms of the discussed patterning of electronic properties within a material, a nematic order mainly influences

Macrocycles and chelating ligands

Another way to lower volatility of a carbon precursor while bringing in local organization which might partly be preserved in the final carbon is by metal coordination and/or salt formation. This is a very classical approach, maybe the oldest known to us to result also in functionally patterned carbons, and for a long time, it is known that carbonization of porphyrines or phtalocyanines gives n-doped carbons with largely increase electrocatalytic activity, e.g. in the oxygen reduction reaction

D–A structures and charge transfer in carbon systems: the role of patches

Switching gears towards patches and superstructures, attractive candidates are the combination of semiconducting (noble) carbon nitride and semimetallic conductive carbons such as graphene.

In this regard, Qiao et al. recently presented the combination of two layered carbons, i.e. carbon nitride as semiconductor and nitrogen-doped graphene as conductor [59]. Here, the carbon nitride was directly grown on graphene oxide films which eventually reduced the latter to nitrogen-doped graphene. The

Summary and future challenges

Exemplified with a variety of cases from the literature including heteroatom-doped carbons, coordination materials and polymers, strategies towards more controlled “designer” carbons were systematized. Three principles for carbon design have been introduced in the beginning which are fundamental to consider when a special effect is to be planned. In general, carbon chemistry is more than “burning your cake” and should be more operated as a controlled condensation with a significant preservation

Nina Fechler studied nanostructure and molecular sciences at the University of Kassel and the Fraunhofer Institute for Applied Polymer Research in Potsdam/Golm (2005–2010) where she was working on thermoresponsive polymers with Dr. Habil. Jean-François Lutz. She obtained her Ph.D. degree from the Max Planck Institute of Colloids and Interfaces in Potsdam/Golm (2010–2013) with Professor Markus Antonietti. During this time, she focused on porous carbon-based materials from ionic liquids for

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    Nina Fechler studied nanostructure and molecular sciences at the University of Kassel and the Fraunhofer Institute for Applied Polymer Research in Potsdam/Golm (2005–2010) where she was working on thermoresponsive polymers with Dr. Habil. Jean-François Lutz. She obtained her Ph.D. degree from the Max Planck Institute of Colloids and Interfaces in Potsdam/Golm (2010–2013) with Professor Markus Antonietti. During this time, she focused on porous carbon-based materials from ionic liquids for energy-related applications and contributed to the establishment of salts as versatile porogens. Afterwards, she continued as a postdoctoral fellow at the same institute (2013) where she worked on supercapacitors and the extension of the salt approach also to other material classes. In this period, she also stayed at the University of California Santa Barbara in the group of Brad Chmelka for solid state NMR investigations of carbon materials. Since 2014, she is research coordinator and group leader at the MPI of Colloids and Interfaces. Her research interest focuses on the sustainable synthesis and processing of carbon nanomaterials for energy storage and conversion using supramolecular self-assembly approaches. Besides science, she has passion for photography, motorbikes and sports.

    Markus Antonietti is director of the Max Planck Institute of Colloids and Interfaces. Starting from polymer science, he now drives modern materials chemistry, where sustainable processes and materials are a central theme. Carbon Materials indeed exert a special fascination to him. He published around 650 Papers and issued 90 patents, his H-index is 124. Besides being a devoted scientist and a higher academic teacher, he also is a passionate chef specialized in fusion cuisine and plays in a Rock ‘n’ Roll band.

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