Tag Archives: defects

The Russians diagnose graphene’s quality and spatial imaging reactivity

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Most of the marvelous things scientists talk about with regard to graphene require a relatively defect-free (perfect) material, from a May 8, 2015 news item on ScienceDaily,

Graphene and related 2D materials are anticipated to become the compounds of the century. It is not surprising — graphene is extremely thin and strong, as well as possesses outstanding electrical and thermal characteristics. The impact of material with such unique properties may be really impressive. Scientists [foresee] the imminent appearance of novel biomedical applications, new generation of smart materials, highly efficient light conversion and photocatalysis reinforced by graphene. However, the stumbling block is that many unique properties and capabilities are related to only perfect graphene with controlled number of defects. [emphasis mine] However, in reality ideal defect-free graphene surface is difficult to prepare and defects may have various sizes and shapes. In addition, dynamic behaviour and fluctuations make the defects difficult to locate. The process of scanning of large areas of graphene sheets in order to find out defect locations and to estimate the quality of the material is a time-consuming task. Let alone a lack of simple direct methods to capture and visualize defects on the carbon surface.

A May 8, 2014 Institute of Organic Chemisty (Russian Academy of Sciences) news release on EurekAlert, which originated the news item, offers more detail about the new technique for determining graphene quality and imaging carbon reactivity centres,

[A] [j]oint research project carried out by Ananikov and co-workers revealed [a] specific contrast agent — soluble palladium complex — that selectively attaches to defect areas on the surface of carbon materials. Pd attachment leads to formation of nanoparti[cl]es, which can be easily detected using a routine electron microscope. The more reactive the carbon center is, the stronger is the binding of contrast agent in the imaging procedure. Thus, reactivity centers and defect sites on a carbon surface were mapped in three-dimensional space with high resolution and excellent contrast using a handy nanoscale imaging procedure. The developed procedure distinguished carbon defects not only due to difference in their morphology, but also due to varying chemical reactivity. Therefore, this imaging approach enables the chemical reactivity to be visualized with spatial resolution.

Mapping carbon reactivity centers with “Pd markers” gave unique insight into the reactivity of the graphene layers. As revealed in the study, more than 2000 reactive centers can be located per 1 μm2 of the surface area of regular carbon material. The study pointed out the spatial complexity of the carbon material at the nanoscale. Mapping of surface defect density showed substantial gradients and variations across the surface area, which can possess a kind of organized structures of defects.

Medical application of imaging (tomography) for diagnostics, including the usage of contrast agents for more accuracy and easier observation, has proven its utility for many years. The present study highlights a new possibility in tomography applications to run diagnostics of materials at atomic scale.

Here’s a link to and a citation for the paper,

Spatial imaging of carbon reactivity centers in Pd/C catalytic systems by E. O. Pentsak, A. S. Kashin, M. V. Polynski, K. O. Kvashnina, P. Glatzel, and V. P. Ananikov.  Chem. Sci., 2015, Advance Article DOI: 10.1039/C5SC00802F
First published online 08 May 2015

This paper is open access.

Grossly warped ‘nanographene’, a brand new type of carbon

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A new of form carbon sounds exciting although the naming convention escapes me. Why call it ‘nanographene’ (albeit grossly warped) when graphene is already nanoscale? (For anyone who can explain this to me, please do let me know.) A July 15, 2013 news release on EurekAlert (it’s also available as a July 15, 2013 news item on ScienceDaily) describes the new form of carbon,

Bucking planarity, contorted sheets of graphene alter physical, optical and electronic properties of new material

Chemists at Boston College and Nagoya University in Japan have synthesized the first example of a new form of carbon, the team reports in the most recent online edition of the journal Nature Chemistry.

The new material consists of multiple identical pieces of grossly warped graphene, each containing exactly 80 carbon atoms joined together in a network of 26 rings, with 30 hydrogen atoms decorating the rim. Because they measure slightly more than a nanometer across, these individual molecules are referred to generically as “nanocarbons,” or more specifically in this case as “grossly warped nanographenes.”

There’s an explanation of why this discovery is special and how it was made (from,the news release),

Until recently, scientists had identified only two forms of pure carbon: diamond and graphite. Then in 1985, chemists were stunned by the discovery that carbon atoms could also join together to form hollow balls, known as fullerenes. Since then, scientists have also learned how to make long, ultra-thin, hollow tubes of carbon atoms, known as carbon nanotubes, and large flat single sheets of carbon atoms, known as graphene. The discovery of fullerenes was awarded the Nobel Prize in Chemistry in 1996, and the preparation of graphene was awarded the Nobel Prize in Physics in 2010.

Graphene sheets prefer planar, 2-dimensional geometries as a consequence of the hexagonal, chicken wire-like, arrangements of trigonal carbon atoms comprising their two-dimensional networks. The new form of carbon just reported in Nature Chemistry, however, is wildly distorted from planarity as a consequence of the presence of five 7-membered rings and one 5-membered ring embedded in the hexagonal lattice of carbon atoms.

Odd-membered-ring defects such as these not only distort the sheets of atoms away from planarity, they also alter the physical, optical, and electronic properties of the material, according to one of the principle authors, Lawrence T. Scott, the Jim and Louise Vanderslice and Family Professor of Chemistry at Boston College.

“Our new grossly warped nanographene is dramatically more soluble than a planar nanographene of comparable size,” said Scott, “and the two differ significantly in color, as well. Electrochemical measurements revealed that the planar and the warped nanographenes are equally easily oxidized, but the warped nanographene is more difficult to reduce.”

… By introducing multiple odd-membered ring defects into the graphene lattice, Scott and his collaborators have experimentally demonstrated that the electronic properties of graphene can be modified in a predictable manner through precisely controlled chemical synthesis.

Here’s a link to and a citation for the paper,

A grossly warped nanographene and the consequences of multiple odd-membered-ring defects by Katsuaki Kawasumi, Qianyan Zhang, Yasutomo Segawa, Lawrence T. Scott, & Kenichiro Itami. Nature Chemistry (2013) doi:10.1038/nchem.1704  Published online 14 July 2013

This paper is behind a paywall. For those who would like more information but can’t get access to the paper at this time, there’s a brief July 15, 2015 news piece by Caryl Richards on the Chemistry World website.