Tag Archives: carbon nanofibres

The birth of carbon nanotubes (CNTs): a history

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There is a comprehensive history of the carbon nanotube stretching back to prehistory and forward to recent times in a June 3, 2016 Nanowerk Spotlight article by C.K. Nisha and Yashwant Mahajan of the Center of Knowledge Management of Nanoscience & Technology (CKMNT) in India. The authors provide an introduction explaining the importance of CNTs,

Carbon nanotubes (CNTs) have been acknowledged as the material of the 21st century. They possess unique combination of extraordinary mechanical, electronic, transport, electrical and optical, properties and nanoscale sizes making them suitable for a variety of applications ranging from engineering, electronics, optoelectronics, photonics, space, defence industry, medicine, molecular and biological systems and so on and so forth. Worldwide demand for CNTs is increasing at a rapid pace as applications for the material are being matured.

According to MarketsandMarkets (M&M), the global market for carbon nanotubes in 2015 was worth about $2.26 billion1; an increase of 45% from 2009 (i.e. ~ $ 1.24 billion). This was due to the growing potential of CNTs in electronics, plastics and energy storage applications and the projected market of CNTs is expected to be around $ 5.64 billion in 2020.

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In view of the scientific and technological potential of CNTs, it is of immense importance to know who should be credited for their discovery. In the present article, we have made an attempt to give a glimpse into the discovery and early history of this fascinating material for our readers. Thousands of papers are being published every year on CNTs or related areas and most of these papers give credit for the discovery of CNTs to Sumio Iijima of NEC Corporation, Japan, who, in 1991, published a ground-breaking paper in Nature reporting the discovery of multi-walled carbon nanotubes (MWCNTs)2. This paper has been cited over 27,105 times in the literature (as on January 12, 2016, based on Scopus database). This discovery by Iijima has triggered an avalanche of scientific publications and catapulted CNTs onto the global scientific stage.

Nisha and Mahajan then prepare to take us back in time,

In a guest editorial for the journal Carbon, Marc Monthioux and Vladimir L. Kuznetsov3 have tried to clear the air by describing the chronological events that led to the discovery of carbon nanotubes. As one delves deeper into the history of carbon nanotubes, it becomes more apparent that the origin of CNTs could be even pre-historic in nature.

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Recently, Ponomarchuk et al from Russia have reported the presence micro and nano carbon tubes in igneous rocks formed about 250 million years ago4-7. They suggested the possibility of formation of carbon nanotubes during the magmatic processes. It is presumed that the migration of hydrocarbon fluids through the residual melt of the rock groundmass created gas-saturated areas (mostly CH4, CO2, CO) in which condensation and decomposition of hydrocarbon in presence of metal elements resulted in the formation of micro and sub-micron carbon tubes.

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Another most compelling evidence of pre-historic naturally occurring carbon nanotubes (MWCNTs) is based on the TEM studies carried out by Esquivel and Murr8 that analyzed 10,000-year-old Greenland ice core samples and it was suggested that probably they could have been formed during combustion of natural gas/methane during natural processes.

However, the validity of this evidence is questionable owing to the lack of clear high-resolution TEM images, high-quality diffraction patterns or Raman spectroscopy data. In addition, [an]other interesting possibility is that the carbon nanotubes could have been directly formed by the transformation of naturally occurring C60 fullerenes in nature without the assistance of man, given the right conditions prevail. Suchanek et al.,9 have actually demonstrated this thesis, under the laboratory environment, by transforming C60 fullerenes into CNTs under hydrothermal conditions.

There is a large body of evidence in literature about the existence of naturally occurring fullerenes in nature, e.g., coal, carboneous rocks, interstellar media, etc. Since the above experiments were conducted under the simulated geological environment, their results imply that CNTs may form in natural hydrothermal environment.

This hypothesis was further corroborated by Velasco-Santos and co-workers10, when they reported the presence of CNTs in a coal–petroleum mix obtained from an actual oil well, identified by the PEMEX (the Mexican Petroleum Company) as P1, which is located in Mexico’s southeast shore. TEM studies revealed that the coal-petroleum mix contained predominantly end-capped CNTs that are nearly 2 µm long with outer diameter varying between few to several tenths of nanometers.

There’s another study supporting the notion that carbon nanotubes may be formed naturally,

In yet another study, researchers from Germany11 have synthesized carbon nanotubes using igneous rock from Mount Etna lava as both support and catalyst. The naturally occurring iron oxide particles present in Etna lava rock make it an ideal material for growing and immobilizing nanocarbons.

When a mixture of ethylene and hydrogen were passed over the pulverized rocks reduced in a hydrogen atmosphere at 700°C, the iron particles catalyzed the decomposition of ethylene to elemental carbon, which gets deposited on the lava rock in the form of tiny tubes and fibers.
This study showed that if a carbon source is available, CNTs/CNFs can grow on a mineral at moderate temperatures, which directs towards the possibilities of carbon nanotube formation in active suboceanic volcanos or even in interstellar space where methane, atomic hydrogen, carbon oxides, and metallic iron are present.

This fascinating and informative piece was originally published in the January 2016 edition of Nanotech Insights (CKMNT newsletter; scroll down) and can be found there although it may be more easily accessible as the June 3, 2016 Nanowerk Spotlight article where it extends over five (Nanowerk) pages and has a number of embedded images along with an extensive list of references at the end.

Enjoy!

Carbon capture with ‘diamonds from the sky’

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Before launching into the latest on a new technique for carbon capture, it might be useful to provide some context. Arthur Neslen’s March 23, 2015 opinion piece outlines the issues and notes that one Norwegian Prime Minister resigned when coalition government partners attempted to build gas power plants without carbon capture and storage facilities (CCS), Note : A link has been removed,

At least 10 European power plants were supposed to begin piping their carbon emissions into underground tombs this year, rather than letting them twirl into the sky. None has done so.

Missed deadlines, squandered opportunities, spiralling costs and green protests have plagued the development of carbon capture and storage (CCS) technology since Statoil proposed the concept more than two decades ago.

But in the face of desperate global warming projections the CCS dream still unites Canadian tar sands rollers with the UN’s Intergovernmental Panel on Climate Change (IPCC), and Shell with some environmentalists.

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With 2bn people in the developing world expected to hook up to the world’s dirty energy system by 2050, CCS holds out the tantalising prospect of fossil-led growth that does not fry the planet.

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“With CCS in the mix, we can decarbonise in a cost-effective manner and still continue to produce, to some extent, our fossil fuels,” Tim Bertels, Shell’s Glocal CCS portfolio manager told the Guardian. “You don’t need to divest in fossil fuels, you need to decarbonise them.”

The technology has been gifted “a very significant fraction” of the billions of dollars earmarked by Shell for clean energy research, he added. But the firm is also a vocal supporter of public funding for CCS from carbon markets, as are almost all players in the industry.

Enthusiasm for this plan is not universal (from Neslen’s opinion piece),

Many environmentalists see the idea as a non-starter because it locks high emitting power plants into future energy systems, and obstructs funding for the cheaper renewables revolution already underway. “CCS is is completely irrelevant,” said Jeremy Rifkin, a noted author and climate adviser to several governments. “I don’t even think about it. It’s not going to happen. It’s not commercially available and it won’t be commercially viable.”

I recommend reading Neslen’s piece for anyone who’s not already well versed on the issues. He uses Norway as a case study and sums up the overall CCS political situation this way,

In many ways, the debate over carbon capture and storage is a struggle between two competing visions of the societal transformation needed to avert climate disaster. One vision represents the enlightened self-interest of a contributor to the problem. The other cannot succeed without eliminating its highly entrenched opponent. The battle is keenly fought by technological optimists on both sides. But if Norway’s fractious CCS experience is any indicator, it will be decided on the ground by the grimmest of realities.

On that note of urgency, here’s some research on carbon dioxide (CO2) or, more specifically, carbon capture and utilization technology, from an Aug. 19, 2015 news item on Nanowerk,,

Finding a technology to shift carbon dioxide (CO2), the most abundant anthropogenic greenhouse gas, from a climate change problem to a valuable commodity has long been a dream of many scientists and government officials. Now, a team of chemists says they have developed a technology to economically convert atmospheric CO2    directly into highly valued carbon nanofibers for industrial and consumer products.

An Aug. 19, 2015 American Chemical Society (ACS) news release (also on EurekAlert), which originated the news time, expands on the theme,

The team will present brand-new research on this new CO2 capture and utilization technology at the 250th National Meeting & Exposition of the American Chemical Society (ACS). ACS is the world’s largest scientific society. The national meeting, which takes place here through Thursday, features more than 9,000 presentations on a wide range of science topics.

“We have found a way to use atmospheric CO2 to produce high-yield carbon nanofibers,” says Stuart Licht, Ph.D., who leads a research team at George Washington University. “Such nanofibers are used to make strong carbon composites, such as those used in the Boeing Dreamliner, as well as in high-end sports equipment, wind turbine blades and a host of other products.”

Previously, the researchers had made fertilizer and cement without emitting CO2, which they reported. Now, the team, which includes postdoctoral fellow Jiawen Ren, Ph.D., and graduate student Jessica Stuart, says their research could shift CO2 from a global-warming problem to a feed stock for the manufacture of in-demand carbon nanofibers.

Licht calls his approach “diamonds from the sky.” That refers to carbon being the material that diamonds are made of, and also hints at the high value of the products, such as the carbon nanofibers that can be made from atmospheric carbon and oxygen.

Because of its efficiency, this low-energy process can be run using only a few volts of electricity, sunlight and a whole lot of carbon dioxide. At its root, the system uses electrolytic syntheses to make the nanofibers. CO2 is broken down in a high-temperature electrolytic bath of molten carbonates at 1,380 degrees F (750 degrees C). Atmospheric air is added to an electrolytic cell. Once there, the CO2 dissolves when subjected to the heat and direct current through electrodes of nickel and steel. The carbon nanofibers build up on the steel electrode, where they can be removed, Licht says.

To power the syntheses, heat and electricity are produced through a hybrid and extremely efficient concentrating solar-energy system. The system focuses the sun’s rays on a photovoltaic solar cell to generate electricity and on a second system to generate heat and thermal energy, which raises the temperature of the electrolytic cell.

Licht estimates electrical energy costs of this “solar thermal electrochemical process” to be around $1,000 per ton of carbon nanofiber product, which means the cost of running the system is hundreds of times less than the value of product output.

“We calculate that with a physical area less than 10 percent the size of the Sahara Desert, our process could remove enough CO2 to decrease atmospheric levels to those of the pre-industrial revolution within 10 years,” he says. [emphasis mine]

At this time, the system is experimental, and Licht’s biggest challenge will be to ramp up the process and gain experience to make consistently sized nanofibers. “We are scaling up quickly,” he adds, “and soon should be in range of making tens of grams of nanofibers an hour.”

Licht explains that one advance the group has recently achieved is the ability to synthesize carbon fibers using even less energy than when the process was initially developed. “Carbon nanofiber growth can occur at less than 1 volt at 750 degrees C, which for example is much less than the 3-5 volts used in the 1,000 degree C industrial formation of aluminum,” he says.

A low energy approach that cleans up the air by converting greenhouse gases into useful materials and does it quickly is incredibly exciting. Of course, there are a few questions to be asked. Are the research outcomes reproducible by other teams? Licht notes the team is scaling the technology up but how soon can we scale up to industrial strength?