Tag Archives: University of the Basque Country (UPV/EHU)

Unraveling carbyne (one-dimensional carbon)

An international group of researchers has developed a technique for producing a record-breaking length of one-dimensional carbon (carbon chain) according to an April 4, 2016 news item on Nanowerk,

Elemental carbon appears in many different modifications, including diamond, fullerenes and graphene. Their unique structural, electronic, mechanical, transport and optical properties have a broad range of applications in physics, chemistry and materials science, including composite materials, nanoscale light emitting devices and energy harvesting materials. Within the “carbon family”, only carbyne, the truly one-dimensional form of carbon, has not yet been synthesized despite having been studied for more than 50 years. Its extreme instability in ambient conditions rendered the final experimental proof of its existence elusive.

An international collaboration of researchers now succeeded in developing a novel route for the bulk production of carbon chains composed of more than 6,400 carbon atoms by using thin double-walled carbon nanotubes as protective hosts for the chains.

An April 4, 2016 University of Vienna press release (also on EurekAlert) provides another perspective on the research,

Even in its elemental form, the high bond versatility of carbon allows for many different well-known materials, including diamond and graphite. A single layer of graphite, termed graphene, can then be rolled or folded into carbon nanotubes or fullerenes, respectively. To date, Nobel prizes have been awarded for both graphene (2010) and fullerenes (1996). Although the existence of carbyne, an infinitely long carbon chain, was proposed in 1885 by Adolf von Baeyer (Nobel laureate for his overall contributions in organic chemistry, 1905), scientists have not yet been able to synthesize this material. Von Baeyer even suggested that carbyne would remain elusive as its high reactivity would always lead to its immediate destruction. Nevertheless, carbon chains of increasing length have been successfully synthesized over the last 50 years, with a record of around 100 carbon atoms (2003). This record has now been broken by more than one order of magnitude, with the demonstration of micrometer length-scale chains.

The new record

Researchers from the University of Vienna, led by Thomas Pichler, have presented a novel approach to grow and stabilize carbon chains with a record length of 6,000 carbon atoms, improving the previous record by more than one order of magnitude. They use the confined space inside a double-walled carbon nanotube as a nano-reactor to grow ultra-long carbon chains on a bulk scale. In collaboration with the groups of Kazu Suenaga at the AIST Tsukuba [National Institute of Advanced Industrial Science and Technology] in Japan, Lukas Novotny at the ETH Zürich [Swiss Federal Institute of Technology] in Switzerland and Angel Rubio at the MPI [Max Planck Institute] Hamburg in Germany and UPV/EHU [University of the Basque Country] San Sebastian in Spain, the existence of the chains has been unambiguously confirmed by using a multitude of sophisticated, complementary methods. These are temperature dependent near- and far-field Raman spectroscopy with different lasers (for the investigation of electronic and vibrational properties), high resolution transmission electron spectroscopy (for the direct observation of carbyne inside the carbon nanotubes) and x-ray scattering (for the confirmation of bulk chain growth).

The researchers present their study in the latest edition of Nature Materials. “The direct experimental proof of confined ultra-long linear carbon chains, which are more than an order of magnitude longer than the longest proven chains so far, can be seen as a promising step towards the final goal of unraveling the “holy grail” of carbon allotropes, carbyne”, explains the lead author, Lei Shi.

Application potential

Carbyne is very stable inside double-walled carbon nanotubes. This property is crucial for its eventual application in future materials and devices. According to theoretical models, carbyne’s mechanical properties exceed all known materials, outperforming both graphene and diamond. Carbyne’s electrical properties suggest novel nanoelectronic applications in quantum spin transport and magnetic semiconductors.

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

Confined linear carbon chains as a route to bulk carbyne by Lei Shi, Philip Rohringer, Kazu Suenaga, Yoshiko Niimi, Jani Kotakoski, Jannik C. Meyer, Herwig Peterlik, Marius Wanko, Seymur Cahangirov, Angel Rubio, Zachary J. Lapin, Lukas Novotny, Paola Ayala, & Thomas Pichler. Nature Materials (2016) doi:10.1038/nmat4617 Published online 04 April 2016

This paper is behind a paywall.

But, there is this earlier and open access version on arXiv.org,

Confined linear carbon chains: A route to bulk carbyne
Lei Shi, Philip Rohringer, Kazu Suenaga, Yoshiko Niimi, Jani Kotakoski, Jannik C. Meyer, Herwig Peterlik, Paola Ayala, Thomas Pichler (Submitted on 17 Jul 2015 (v1), last revised 20 Jul 2015 (this version, v2))

PlasCarb: producing graphene and renewable hydrogen from food waster

I have two tidbits about PlasCarb the first being an announcement of its existence and the second an announcement of its recently published research. A Jan. 13, 2015 news item on Nanowerk describes the PlasCarb project (Note: A link has been removed),

The Centre for Process Innovation (CPI) is leading a European collaborative project that aims to transform food waste into a sustainable source of significant economic added value, namely graphene and renewable hydrogen.

The project titled PlasCarb will transform biogas generated by the anaerobic digestion of food waste using an innovative low energy microwave plasma process to split biogas (methane and carbon dioxide) into high value graphitic carbon and renewable hydrogen.

A Jan. 13, 2015 CPI press release, which originated the news item, describes the project and its organization in greater detail,

CPI  as the coordinator of the project is responsible for the technical aspects in the separation of biogas into methane and carbon dioxide, and separating of the graphitic carbon produced from the renewable hydrogen. The infrastructure at CPI allows for the microwave plasma process to be trialled and optimised at pilot production scale, with a future technology roadmap devised for commercial scale manufacturing.

Graphene is one of the most interesting inventions of modern times. Stronger than steel, yet light, the material conducts electricity and heat. It has been used for a wide variety of applications, from strengthening tennis rackets, spray on radiators, to building semiconductors, electric circuits and solar cells.

The sustainable creation of graphene and renewable hydrogen from food waste in provides a sustainable method towards dealing with food waste problem that the European Union faces. It is estimated that 90 million tonnes of food is wasted each year, a figure which could rise to approximately 126 million tonnes by 2020. In the UK alone, food waste equates to a financial loss to business of at least £5 billion per year.

Dr Keith Robson, Director of Formulation and Flexible Manufacturing at CPI said, “PlasCarb will provide an innovative solution to the problems associated with food waste, which is one of the biggest challenges that the European Union faces in the strive towards a low carbon economy.  The project will not only seek to reduce food waste but also use new technological methods to turn it into renewable energy resources which themselves are of economic value, and all within a sustainable manner.”

PlasCarb will utilise quality research and specialist industrial process engineering to optimise the quality and economic value of the Graphene and hydrogen, further enhancing the sustainability of the process life cycle.

Graphitic carbon has been identified as one of Europe’s economically critical raw materials and of strategic performance in the development of future emerging technologies. The global market for graphite, either mined or synthetic is worth over €10 billion per annum. Hydrogen is already used in significant quantities by industry and recognised with great potential as a future transport fuel for a low carbon economy. The ability to produce renewable hydrogen also has added benefits as currently 95% of hydrogen is produced from fossil fuels. Moreover, it is currently projected that increasing demand of raw materials from fossil sources will lead to price volatility, accelerated environmental degradation and rising political tensions over resource access.

Therefore, the latter stages of the project will be dedicated to the market uptake of the PlasCarb process and the output products, through the development of an economically sustainable business strategy, a financial risk assessment of the project results and a flexible financial model that is able to act as a primary screen of economic viability. Based on this, an economic analysis of the process will be determined. Through the development of a decentralised business model for widespread trans-European implementation, the valorisation of food waste will have the potential to be undertaken for the benefit of local economies and employment. More specifically, three interrelated post project exploitation markets have been defined: food waste management, high value graphite and RH2 sales.

PlasCarb is a 3-year collaborative project, co-funded under the European Union’s Seventh Framework Programme (FP7) and will further reinforce Europe’s leading position in environmental technologies and innovation in high value Carbon. The consortium is composed of eight partners led by CPI from five European countries, whose complimentary research and industrial expertise will enable the required results to be successfully delivered. The project partners are; The Centre for Process Innovation (UK), GasPlas AS (NO), CNRS (FR), Fraunhofer IBP (DE), Uvasol Ltd (UK), GAP Waste Management (UK), Geonardo Ltd. (HU), Abalonyx AS (NO).

You can find PlasCarb here.

The second announcement can be found in a PlasCarb Jan. 14, 2015 press release announcing the publication of research on heterostructures of graphene ribbons,

Few materials have received as much attention from the scientific world or have raised so many hopes with a view to their potential deployment in new applications as graphene has. This is largely due to its superlative properties: it is the thinnest material in existence, almost transparent, the strongest, the stiffest and at the same time the most strechable, the best thermal conductor, the one with the highest intrinsic charge carrier mobility, plus many more fascinating features. Specifically, its electronic properties can vary enormously through its confinement inside nanostructured systems, for example. That is why ribbons or rows of graphene with nanometric widths are emerging as tremendously interesting electronic components. On the other hand, due to the great variability of electronic properties upon minimal changes in the structure of these nanoribbons, exact control on an atomic level is an indispensable requirement to make the most of all their potential.

The lithographic techniques used in conventional nanotechnology do not yet have such resolution and precision. In the year 2010, however, a way was found to synthesise nanoribbons with atomic precision by means of the so-called molecular self-assembly. Molecules designed for this purpose are deposited onto a surface in such a way that they react with each other and give rise to perfectly specified graphene nanoribbons by means of a highly reproducible process and without any other external mediation than heating to the required temperature. In 2013 a team of scientists from the University of Berkeley and the Centre for Materials Physics (CFM), a mixed CSIC (Spanish National Research Council) and UPV/EHU (University of the Basque Country) centre, extended this very concept to new molecules that were forming wider graphene nanoribbons and therefore with new electronic properties. This same group has now managed to go a step further by creating, through this self-assembly, heterostructures that blend segments of graphene nanoribbons of two different widths.

The forming of heterostructures with different materials has been a concept widely used in electronic engineering and has enabled huge advances to be made in conventional electronics. “We have now managed for the first time to form heterostructures of graphene nanoribbons modulating their width on a molecular level with atomic precision. What is more, their subsequent characterisation by means of scanning tunnelling microscopy and spectroscopy, complemented with first principles theoretical calculations, has shown that it gives rise to a system with very interesting electronic properties which include, for example, the creation of what are known as quantum wells,” pointed out the scientist Dimas de Oteyza, who has participated in this project. This work, the results of which are being published this very week in the journal Nature Nanotechnology, therefore constitutes a significant success towards the desired deployment of graphene in commercial electronic applications.

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

Molecular bandgap engineering of bottom-up synthesized graphene nanoribbon heterojunctions by Yen-Chia Chen, Ting Cao, Chen Chen, Zahra Pedramrazi, Danny Haberer, Dimas G. de Oteyza, Felix R. Fischer, Steven G. Louie, & Michael F. Crommie. Nature Nanotechnology (2015) doi:10.1038/nnano.2014.307 Published online 12 January 2015

This article is behind a paywall but there is a free preview available via ReadCube access.