Tag Archives: carbon nanostructures

Interstellar buckyball mystery solved

Caption: An artist’s conception showing spherical carbon molecules known as buckyballs coming out from a planetary nebula — material shed by a dying star. Researchers at the University of Arizona have now created these molecules under laboratory conditions thought to mimic those in their ‘natural’ habitat in space. Credit: NASA/JPL-Caltech

A ‘buckyball’, for anyone who doesn’t know, is a molecule made up of carbon atoms, Said to resemble soccer balls or geodesic domes, they’re also known as C60 or Buckminsterfullerenes as Rachel Abraham notes in her November 13, 2019 University of Arizona news release (also on EurekAlert),

Scientists have long been puzzled by the existence of so-called “buckyballs” – complex carbon molecules with a soccer-ball-like structure – throughout interstellar space. Now, a team of researchers from the University of Arizona has proposed a mechanism for their formation in a study published in the Astrophysical Journal Letters.

Carbon 60, or C60 for short, whose official name is Buckminsterfullerene, comes in spherical molecules consisting of 60 carbon atoms organized in five-membered and six-membered rings. The name “buckyball” derives from their resemblance to the architectural work of Richard Buckminster Fuller [bettr known as Buckminster Fuller], who designed many dome structures that look similar to C60. Their formation was thought to only be possible in lab settings until their detection in space challenged this assumption.

For decades, people thought interstellar space was sprinkled with lightweight molecules only: mostly single atoms, two-atom molecules and the occasional nine or 10-atom molecules. This was until massive C60 and C70 molecules were detected a few years ago.

Researchers were also surprised to find that that they were composed of pure carbon. In the lab, C60 is made by blasting together pure carbon sources, such as graphite. In space, C60 was detected in planetary nebulae, which are the debris of dying stars. This environment has about 10,000 hydrogen molecules for every carbon molecule.

“Any hydrogen should destroy fullerene synthesis,” said astrobiology and chemistry doctoral student Jacob Bernal, lead author of the paper. “If you have a box of balls, and for every 10,000 hydrogen balls you have one carbon, and you keep shaking them, how likely is it that you get 60 carbons to stick together? It’s very unlikely.”

Bernal and his co-authors began investigating the C60 mechanism after realizing that the transmission electron microscope, or TEM, housed at the Kuiper Materials Imaging and Characterization Facility at UArizona, was able to simulate the planetary nebula environment fairly well.

The TEM, which is funded by the National Science Foundation and NASA, has a serial number of “1” because it is the first of its kind in the world with its exact configuration. Its 200,000-volt electron beam can probe matter down to 78 picometers – scales too small for the human brain to comprehend – in order to see individual atoms. It operates under a vacuum with extremely low pressures. This pressure, or lack thereof, in the TEM is very close to the pressure in circumstellar environments.

“It’s not that we necessarily tailored the instrument to have these specific kinds of pressures,” said Tom Zega, associate professor in the UArizona Lunar and Planetary Lab and study co-author. “These instruments operate at those kinds of very low pressures not because we want them to be like stars, but because molecules of the atmosphere get in the way when you’re trying to do high-resolution imaging with electron microscopes.”

The team partnered with the U.S. Department of Energy’s Argonne National Lab, near Chicago, which has a TEM capable of studying radiation responses of materials. They placed silicon carbide, a common form of dust made in stars, in the low-pressure environment of the TEM, subjected it to temperatures up to 1,830 degrees Fahrenheit and irradiated it with high-energy xenon ions.

Then, it was brought back to Tucson for researchers to utilize the higher resolution and better analytical capabilities of the UArizona TEM. They knew their hypothesis would be validated if they observed the silicon shedding and exposing pure carbon.

“Sure enough, the silicon came off, and you were left with layers of carbon in six-membered ring sets called graphite,” said co-author Lucy Ziurys, Regents Professor of astronomy, chemistry and biochemistry. “And then when the grains had an uneven surface, five-membered and six-membered rings formed and made spherical structures matching the diameter of C60. So, we think we’re seeing C60.”

This work suggests that C60 is derived from the silicon carbide dust made by dying stars, which is then hit by high temperatures, shockwaves and high energy particles , leeching silicon from the surface and leaving carbon behind. These big molecules are dispersed because dying stars eject their material into the interstellar medium – the spaces in between stars – thus accounting for their presence outside of planetary nebulae. Buckyballs are very stable to radiation, allowing them to survive for billions of years if shielded from the harsh environment of space.

“The conditions in the universe where we would expect complex things to be destroyed are actually the conditions that create them,” Bernal said, adding that the implications of the findings are endless.

“If this mechanism is forming C60, it’s probably forming all kinds of carbon nanostructures,” Ziurys said. “And if you read the chemical literature, these are all thought to be synthetic materials only made in the lab, and yet, interstellar space seems to be making them naturally.”

If the findings are any sign, it appears that there is more the universe has to tell us about how chemistry truly works.

I have two links and citations. This first is for the 2019 paper being described here and the second is the original 1985 paper about C60.

Formation of Interstellar C60 from Silicon Carbide Circumstellar Grains by J. J. Bernal, P. Haenecour, J. Howe, T. J. Zega, S. Amari, and L. M. Ziurys. The Astrophysical Journal Letters, Volume 883, Number 2 Published 2019 October 1 © 2019. The American Astronomical Society. All rights reserved.

This paper is behind a paywall.

C60: Buckminsterfullerene by H. W. Kroto, J. R. Heath, S. C. O’Brien, R. F. Curl & R. E. Smalley. Nature volume 318, pages162–163 (1985) doi:10.1038/318162a0

This paper is open access.

Figuring out how stars are born by watching neutrons ‘quantum tunnelling’ on graphene

A Feb. 3, 2017 news item on Nanowerk announces research that could help us better understand how stars are ‘born’,

Graphene is known as the world’s thinnest material due to its 2D structure, where each sheet is only one carbon atom thick, allowing each atom to engage in a chemical reaction from two sides. Graphene flakes can have a very large proportion of edge atoms, all of which have a particular chemical reactivity.

In addition, chemically active voids created by missing atoms are a surface defect of graphene sheets. These structural defects and edges play a vital role in carbon chemistry and physics, as they alter the chemical reactivity of graphene. In fact, chemical reactions have repeatedly been shown to be favoured at these defect sites.

Interstellar molecular clouds are predominantly composed of hydrogen in molecular form (H2), but also contain a small percentage of dust particles mostly in the form of carbon nanostructures, called polyaromatic hydrocarbons (PAH). These clouds are often referred to as ‘star nurseries’ as their low temperature and high density allows gravity to locally condense matter in such a way that it initiates H fusion, the nuclear reaction at the heart of each star.

Graphene-based materials, prepared from the exfoliation of graphite oxide, are used as a model of interstellar carbon dust as they contain a relatively large amount of atomic defects, either at their edges or on their surface. These defects are thought to sustain the Eley-Rideal chemical reaction, which recombines two H atoms into one H2 molecule. The observation of interstellar clouds in inhospitable regions of space, including in the direct proximity of giant stars, poses the question of the origin of the stability of hydrogen in the molecular form (H2).

This question stands because the clouds are constantly being washed out by intense radiation, hence cracking the hydrogen molecules into atoms. Astrochemists suggest that the chemical mechanism responsible for the recombination of atomic H into molecular H2 is catalysed by carbon flakes in interstellar clouds.

A Feb. 2, 2017 Institut Laue-Langevin press release, which originated the news item, provides more insight into the research,

Their [astrochemists’s] theories are challenged by the need for a very efficient surface chemistry scenario to explain the observed equilibrium between dissociation and recombination. They had to introduce highly reactive sites into their models so that the capture of an atomic H nearby occurs without fail. These sites, in the form of atomic defects at the surface or edge of the carbon flakes, should be such that the C-H bond formed thereafter allows the H atom to be released easily to recombine with another H atom flying nearby.

A collaboration between the Institut Laue-Langevin (ILL), France, the University of Parma, Italy, and the ISIS Neutron and Muon Source, UK, combined neutron spectroscopy with density functional theory (DFT) molecular dynamics simulations in order to characterise the local environment and vibrations of hydrogen atoms chemically bonded at the surface of substantially defected graphene flakes. Additional analyses were carried out using muon spectroscopy (muSR) and nuclear magnetic resonance (NMR). As availability of the samples is very low, these highly specific techniques were necessary to study the samples; neutron spectroscopy is highly sensitive to hydrogen and allowed accurate data to be gathered at small concentrations.

For the first time ever, this study showed ‘quantum tunnelling’ in these systems, allowing the H atoms bound to C atoms to explore relatively long distances at temperatures as low as those in interstitial clouds. The process involves hydrogen ‘quantum hopping’ from one carbon atom to another in its direct vicinity, tunnelling through energy barriers which could not be overcome given the lack of heat in the interstellar cloud environment. This movement is sustained by the fluctuations of the graphene structure, which bring the H atom into unstable regions and catalyse the recombination process by allowing the release of the chemically bonded H atom. Therefore, it is believed that quantum tunnelling facilitates the reaction for the formation of molecular H2.

ILL scientist and carbon nanostructure specialist, Stéphane Rols says: “The question of how molecular hydrogen forms at the low temperatures in interstellar clouds has always been a driver in astrochemistry research. We’re proud to have combined spectroscopy expertise with the sensitivity of neutrons to identify the intriguing quantum tunnelling phenomenon as a possible mechanism behind the formation of H2; these observations are significant in furthering our understanding of the universe.”

Here’s a link to and a citation for the paper (which dates from Aug. 2016),

Hydrogen motions in defective graphene: the role of surface defects by Chiara Cavallari, Daniele Pontiroli, Mónica Jiménez-Ruiz, Mark Johnson, Matteo Aramini, Mattia Gaboardi, Stewart F. Parker, Mauro Riccó, and Stéphane Rols. Phys. Chem. Chem. Phys., 2016, Issue 36, 18, 24820-24824 DOI: 10.1039/C6CP04727K First published online 22 Aug 2016

This paper is behind a paywall.