Tag Archives: James M. Tour

Like water for graphene nanoribbons

Reference to magical realism and fiction aside (Like Water for Chocolate by Laura Esquivel), it turns out that water is integral to the formation of very long, very thin graphene nanoribbons. A July 30, 2011 Rice University news release describes the phenomenon, a two year research odyssey, and the scientific ‘accident’ which led researchers to the discovery,

New research at Rice University shows how water makes it practical to form long graphene nanoribbons less than 10 nanometers wide.

And it’s unlikely that many of the other labs currently trying to harness the potential of graphene, a single-atom sheet of carbon, for microelectronics would have come up with the technique the Rice researchers found while they were looking for something else.

The discovery by lead author Vera Abramova and co-author Alexander Slesarev, both graduate students in the lab of Rice chemist James Tour, appears online this month in the American Chemical Society journal ACS Nano.

A bit of water adsorbed from the atmosphere was found to act as a mask in a process that begins with the creation of patterns via lithography and ends with very long, very thin graphene nanoribbons. The ribbons form wherever water gathers at the wedge between the raised pattern and the graphene surface.

The water formation is called a meniscus; it is created when the surface tension of a liquid causes it to curve [in a convex or concave manner]. In the Rice process, the meniscus mask protects a tiny ribbon of graphene from being etched away when the pattern is removed.

Tour said any method to form long wires only a few nanometers wide should catch the interest of microelectronics manufacturers as they approach the limits of their ability to miniaturize circuitry. “They can never take advantage of the smallest nanoscale devices if they can’t address them with a nanoscale wire,” he said. “Right now, manufacturers can make small features, or make big features and put them where they want them. But to have both has been difficult. To be able to pattern a line this thin right where you want it is a big deal because it permits you to take advantage of the smallness in size of nanoscale devices.”

Tour said water’s tendency to adhere to surfaces is often annoying, but in this case it’s essential to the process. “There are big machines that are used in electronics research that are often heated to hundreds of degrees under ultrahigh vacuum to drive off all the water that adheres to the inside surfaces,” he said. “Otherwise there’s always going to be a layer of water. In our experiments, water accumulates at the edge of the structure and protects the graphene from the reactive ion etching (RIE). So in our case, that residual water is the key to success.

Abramova and Slesarev had set out to fabricate nanoribbons by inverting a method developed by another Rice lab to make narrow gaps in materials. The original method utilized the ability of some metals to form a native oxide layer that expands and shields material just on the edge of the metal mask. The new method worked, but not as expected.

“We first suspected there was some kind of shadowing,” Abramova said. But other metals that didn’t expand as much, if at all, showed no difference, nor did varying the depth of the pattern. “I was basically looking for anything that would change something.”

It took two years to develop and test the meniscus theory, during which the researchers also confirmed its potential to create sub-10-nanometer wires from other kinds of materials, including platinum. They also constructed field-effect transistors to check the electronic properties of graphene nanoribbons.

To be sure that water does indeed account for the ribbons, they tried eliminating its effect by first drying the patterns by heating them under vacuum, and then by displacing the water with acetone to eliminate the meniscus. In both cases, no graphene nanoribbons were created.

The researchers are working to better control the nanoribbons’ width, and they hope to refine the nanoribbons’ edges, which help dictate their electronic properties.

“With this study, we figured out you don’t need expensive tools to get these narrow features,” Tour said. “You can use the standard tools [;] a fab line already has to make features that are smaller than 10 nanometers.”

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

Meniscus-Mask Lithography for Narrow Graphene Nanoribbons by Vera Abramova, Alexander S. Slesarev, and James M. Tour. ACS Nano, Article ASAP DOI: 10.1021/nn403057t Publication Date (Web): July 23, 2013
Copyright © 2013 American Chemical Society

This paper is behind a paywall.

Dexter Johnson in his July30, 2013 posting on the Nanoclast blog (on the IEEE [Institute of Electrical and Electronics Engineers]) notes that this use of water is counter-intuitive,

In [an] ironic twist, the water that most lithography processes try avoid and eliminate at great cost is the same water that makes this new lithography process work.

Graphene and radioactive waste

In fact, the material in question is graphene oxide and researchers at Rice University (Texas) and Lomonosov Moscow State University have found that it can rapidly remove radioactive material from water  From the Jan. 8, 2013 news item on ScienceDaily,

A collaborative effort by the Rice lab of chemist James Tour and the Moscow lab of chemist Stepan Kalmykov determined that microscopic, atom-thick flakes of graphene oxide bind quickly to natural and human-made radionuclides and condense them into solids. The flakes are soluble in liquids and easily produced in bulk.

The Rice University Jan. 8, 2013 news release, which originated the news item, was written by Mike Williams and provides additional insight and quotes from the researchers (Note: Links have been removed),

The discovery, Tour said, could be a boon in the cleanup of contaminated sites like the Fukushima nuclear plants damaged by the 2011 earthquake and tsunami. It could also cut the cost of hydraulic fracturing (“fracking”) for oil and gas recovery and help reboot American mining of rare earth metals, he said.

Graphene oxide’s large surface area defines its capacity to adsorb toxins, Kalmykov said. “So the high retention properties are not surprising to us,” he said. “What is astonishing is the very fast kinetics of sorption, which is key.”

“In the probabilistic world of chemical reactions where scarce stuff (low concentrations) infrequently bumps into something with which it can react, there is a greater likelihood that the ‘magic’ will happen with graphene oxide than with a big old hunk of bentonite,” said Steven Winston, a former vice president of Lockheed Martin and Parsons Engineering and an expert in nuclear power and remediation who is working with the researchers. “In short, fast is good.”

Here’s how it works (from the news release; Note: Links have been removed),

The researchers focused on removing radioactive isotopes of the actinides  and lanthanides  – the 30 rare earth elements in the periodic table – from liquids, rather than solids or gases. “Though they don’t really like water all that much, they can and do hide out there,” Winston said. “From a human health and environment point of view, that’s where they’re least welcome.”

Naturally occurring radionuclides are also unwelcome in fracking fluids that bring them to the surface in drilling operations, Tour said. “When groundwater comes out of a well and it’s radioactive above a certain level, they can’t put it back into the ground,” he said. “It’s too hot. Companies have to ship contaminated water to repository sites around the country at very large expense.” The ability to quickly filter out contaminants on-site would save a great deal of money, he said.

He sees even greater potential benefits for the mining industry. Environmental requirements have “essentially shut down U.S. mining of rare earth metals, which are needed for cell phones,” Tour said. “China owns the market because they’re not subject to the same environmental standards. So if this technology offers the chance to revive mining here, it could be huge.”

Tour said that capturing radionuclides does not make them less radioactive, just easier to handle. “Where you have huge pools of radioactive material, like at Fukushima, you add graphene oxide and get back a solid material from what were just ions in a solution,” he said. “Then you can skim it off and burn it. Graphene oxide burns very rapidly and leaves a cake of radioactive material you can then reuse.”

The low cost and biodegradable qualities of graphene oxide should make it appropriate for use in permeable reactive barriers, a fairly new technology for in situ groundwater remediation, he said.

Romanchuk, Slesarev, Kalmykov and Tour are co-authors of the paper with Dmitry Kosynkin, a former postdoctoral researcher at Rice, now with Saudi Aramco. Kalmykov is radiochemistry division head and a professor at Lomonosov Moscow State University. Tour is the T.T. and W.F. Chao Chair in Chemistry as well as a professor of mechanical engineering and materials science and of computer science at Rice.

Here’s a ‘before’ shot of solution with graphene oxide and an ‘after’ shot where radionuclides have been added and begun to clump,

A new method for removing radioactive material from solutions is the result of collaboration between Rice University and Lomonosov Moscow State University. The vial at left holds microscopic particles of graphene oxide in a solution. At right, graphene oxide is added to simulated nuclear waste, which quickly clumps for easy removal. Image by Anna Yu. Romanchuk/Lomonosov Moscow State University

A new method for removing radioactive material from solutions is the result of collaboration between Rice University and Lomonosov Moscow State University. The vial at left holds microscopic particles of graphene oxide in a solution. At right, graphene oxide is added to simulated nuclear waste, which quickly clumps for easy removal. Image by Anna Yu. Romanchuk/Lomonosov Moscow State University

As noted in the ScienceDaily news item, the research has been published in the Royal Society’s Physical Chemistry Chemical Physics journal,

Anna Yu. Romanchuk, Alexander Slesarev, Stepan N. Kalmykov, Dmitry Kosynkin, James M Tour. Graphene Oxide for Effective Radionuclide Removal. Physical Chemistry Chemical Physics, 2012; DOI: 10.1039/C2CP44593J

This article is behind a paywall.

James’ bond (Rice University research team creates graphene/nanotube hybrid)

I have to give credit to Mike Williams’ Nov. 27, 2012 Rice University news release for the “James’ bond” phrase used to describe this graphene/nanotube hybrid,

A seamless graphene/nanotube hybrid created at Rice University may be the best electrode interface material possible for many energy storage and electronics applications.

Led by Rice chemist James Tour, researchers have successfully grown forests of carbon nanotubes that rise quickly from sheets of graphene to astounding lengths of up to 120 microns, according to a paper published today by Nature Communications. A house on an average plot with the same aspect ratio would rise into space.

Seven-atom rings (in red) at the transition from graphene to nanotube make this new hybrid material a seamless conductor. The hybrid may be the best electrode interface material possible for many energy storage and electronics applications. Image courtesy of the Tour Group

The Rice hybrid combines two-dimensional graphene, which is a sheet of carbon one atom thick, and nanotubes into a seamless three-dimensional structure. The bonds between them are covalent, which means adjacent carbon atoms share electrons in a highly stable configuration. The nanotubes aren’t merely sitting on the graphene sheet; they become a part of it.

“Many people have tried to attach nanotubes to a metal electrode and it’s never gone very well because they get a little electronic barrier right at the interface,” Tour said. “By growing graphene on metal (in this case copper) and then growing nanotubes from the graphene, the electrical contact between the nanotubes and the metal electrode is ohmic. That means electrons see no difference, because it’s all one seamless material.

In the new work, the team grew a specialized odako that retained the iron catalyst and aluminum oxide buffer but put them on top of a layer of graphene grown separately on a copper substrate. The copper stayed to serve as an excellent current collector for the three-dimensional hybrids that were grown within minutes to controllable lengths of up to 120 microns.

Electron microscope images showed the one-, two- and three-walled nanotubes firmly embedded in the graphene, and electrical testing showed no resistance to the flow of current at the junction.

“The performance we see in this study is as good as the best carbon-based supercapacitors that have ever been made,” Tour said. “We’re not really a supercapacitor lab, and still we were able to match the performance because of the quality of the electrode. It’s really remarkable, and it all harkens back to that unique interface.”

Here’s the citation and a link for the article,

A seamless three-dimensional carbon nanotube graphene hybrid material by Yu Zhu, Lei Li, Chenguang Zhang, Gilberto Casillas,  Zhengzong Sun, Zheng Yan, Gedeng Ruan, Zhiwei Peng, Abdul-Rahman O. Raji, Carter Kittrell, Robert H. Hauge & James M. Tour in Nature Communications 3, Article number:1225 doi:10.1038/ncomms2234 Published 27 November 2012

This article is behind a paywall.

Antioxidant-like carbon nanoparticles could help heal traumatic brain injuries

The research sounds exciting but all of the testing has taken place in laboratories on animal models (rats). The Oct. 18, 2012 news item on Azonano describes why the research team wanted to test  antioxidant-like carbon nanotubes for use with traumatic brain injury (TBI) patients,

Thomas Kent, James Tour and colleagues explain that TBI disrupts the supply of oxygen-rich blood to the brain. With the brain so oxygen-needy — accounting for only 2 percent of a person’s weight, but claiming 20 percent of the body’s oxygen supply — even a mild injury, such as a concussion, can have serious consequences. Reduced blood flow and resuscitation result in a build-up of free-radicals, which can kill brain cells. Despite years of far-ranging efforts, no effective treatment has emerged for TBI. That’s why the scientists tried a new approach, based on nanoparticles so small that 1000 would fit across the width of a human hair.

The American Chemical Society (ACS) Oct. 17, 2912 news release, which originated the news item, provides a few details about the research,

They [the research team]  describe development and successful laboratory tests of nanoparticles, called PEG-HCCs. In laboratory rats, the nanoparticles acted like antioxidants, rapidly restoring blood flow to the brain following resuscitation after TBI. “This finding is of major importance for improving patient health under clinically relevant conditions during resuscitative care, and it has direct implications for the current [TBI] war-fighter victims in the Afghanistan and Middle East theaters,” they say.

The abstract for the paper gives more insight,

Injury to the neurovasculature is a feature of brain injury and must be addressed to maximize opportunity for improvement. Cerebrovascular dysfunction, manifested by reduction in cerebral blood flow (CBF), is a key factor that worsens outcome after traumatic brain injury (TBI), most notably under conditions of hypotension. We report here that a new class of antioxidants, poly(ethylene glycol)-functionalized hydrophilic carbon clusters (PEG-HCCs), which are nontoxic carbon particles, rapidly restore CBF in a mild TBI/hypotension/resuscitation rat model when administered during resuscitation—a clinically relevant time point. Along with restoration of CBF, there is a concomitant normalization of superoxide and nitric oxide levels. Given the role of poor CBF in determining outcome, this finding is of major importance for improving patient health under clinically relevant conditions during resuscitative care, and it has direct implications for the current TBI/hypotension war-fighter victims in the Afghanistan and Middle East theaters. The results also have relevancy in other related acute circumstances such as stroke and organ transplantation.

I notice this treatment has shown some success for mildTBI/hypotension if applied in the resuscitation phase and the testing, as I mentioned earlier, has been done on rats. For anyone who wants more information about this promising treatment,

Antioxidant Carbon Particles Improve Cerebrovascular Dysfunction Following Traumatic Brain Injury by Brittany R. Bitner, Daniela C. Marcano, Jacob M. Berlin, Roderic H. Fabian, Leela Cherian, James C. Culver, Mary E. Dickinson, Claudia S. Robertson, Robia G. Pautler, Thomas A. Kent, and James M. Tour. ACS Nano, 2012, 6 (9), pp 8007–8014 DOI: 10.1021/nn302615f

The article is behind a paywall and I notice it was published online Aug. 6, 2012. It looks like the ACS may may have tried to publicize this at the time of publication and decided to try again now in the hope of getting more publicity for this work.