Rice University Expands LIG (laser induced graphene) Research and Applications: Supercapacitor, an Electrocatalyst for Fuel Cells, RFID’s and Biological Sensors


J Tour Graphene on Toast 162948_webIMAGE: THIS IS RICE UNIVERSITY GRADUATE STUDENT YIEU CHYAN, LEFT, AND PROFESSOR JAMES TOUR. view more  CREDIT: JEFF FITLOW/RICE UNIVERSITY

Rice University scientists who introduced laser-induced graphene (LIG) have enhanced their technique to produce what may become a new class of edible electronics.

The Rice lab of chemist James Tour, which once turned Girl Scout cookies into graphene, is investigating ways to write graphene patterns onto food and other materials to quickly embed conductive identification tags and sensors into the products themselves.

“This is not ink,” Tour said. “This is taking the material itself and converting it into graphene.”

The process is an extension of the Tour lab’s contention that anything with the proper carbon content can be turned into graphene. In recent years, the lab has developed and expanded upon its method to make graphene foam by using a commercial laser to transform the top layer of an inexpensive polymer film.

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Laser-Induced graphene supercapacitors may be the future of wearables

The foam consists of microscopic, cross-linked flakes of graphene, the two-dimensional form of carbon. LIG can be written into target materials in patterns and used as a supercapacitor, an electrocatalyst for fuel cells, radio-frequency identification (RFID) antennas and biological sensors, among other potential applications.

The new work reported in the American Chemical Society journal ACS Nano demonstrated that laser-induced graphene can be burned into paper, cardboard, cloth, coal and certain foods, even toast.

“Very often, we don’t see the advantage of something until we make it available,” Tour said. “Perhaps all food will have a tiny RFID tag that gives you information about where it’s been, how long it’s been stored, its country and city of origin and the path it took to get to your table.”

He said LIG tags could also be sensors that detect E. coli or other microorganisms on food. “They could light up and give you a signal that you don’t want to eat this,” Tour said. “All that could be placed not on a separate tag on the food, but on the food itself.”

Multiple laser passes with a defocused beam allowed the researchers to write LIG patterns into cloth, paper, potatoes, coconut shells and cork, as well as toast. (The bread is toasted first to “carbonize” the surface.) The process happens in air at ambient temperatures.

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“In some cases, multiple lasing creates a two-step reaction,” Tour said. “First, the laser photothermally converts the target surface into amorphous carbon. Then on subsequent passes of the laser, the selective absorption of infrared light turns the amorphous carbon into LIG. We discovered that the wavelength clearly matters.”

The researchers turned to multiple lasing and defocusing when they discovered that simply turning up the laser’s power didn’t make better graphene on a coconut or other organic materials. But adjusting the process allowed them to make a micro supercapacitor in the shape of a Rice “R” on their twice-lased coconut skin.

Defocusing the laser sped the process for many materials as the wider beam allowed each spot on a target to be lased many times in a single raster scan. That also allowed for fine control over the product, Tour said. Defocusing allowed them to turn previously unsuitable polyetherimide into LIG.

“We also found we could take bread or paper or cloth and add fire retardant to them to promote the formation of amorphous carbon,” said Rice graduate student Yieu Chyan, co-lead author of the paper. “Now we’re able to take all these materials and convert them directly in air without requiring a controlled atmosphere box or more complicated methods.”

The common element of all the targeted materials appears to be lignin, Tour said. An earlier study relied on lignin, a complex organic polymer that forms rigid cell walls, as a carbon precursor to burn LIG in oven-dried wood. Cork, coconut shells and potato skins have even higher lignin content, which made it easier to convert them to graphene.

Tour said flexible, wearable electronics may be an early market for the technique. “This has applications to put conductive traces on clothing, whether you want to heat the clothing or add a sensor or conductive pattern,” he said.

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Rice alumnus Ruquan Ye is co-lead author of the study. Co-authors are Rice graduate student Yilun Li and postdoctoral fellow Swatantra Pratap Singh and Professor Christopher Arnusch of Ben-Gurion University of the Negev, Israel. Tour is the T.T. and W.F. Chao Chair in Chemistry as well as a professor of computer science and of materials science and nanoengineering at Rice.

The Air Force Office of Scientific Research supported the research.

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Rice University: NEWT: New One-Step Catalyst Converts Nitrates to Water and Air


Rice Water Air Nitrates 159751_webRice University’s indium-palladium nanoparticle catalysts clean nitrates from drinking water by converting the toxic molecules into air and water. Credit Jeff Fitlow/Rice University

A simple, one-step catalyst could help yield cleaner drinking water with less nitrates.

A team from Rice University’s Nanotechnology Enabled Water Treatment (NEWT) Center have discovered that a catalyst made from indium and palladium can clean toxic nitrates from drinking water by converting them into air and water.

“Indium likes to be oxidized,” co-author Kim Heck, a research scientist at Rice, said in a statement. “From our in situ studies, we found that exposing the catalysts to solutions containing nitrate caused the indium to become oxidized.

“But when we added hydrogen-saturated water, the palladium prompted some of that oxygen to bond with the hydrogen and form water, and that resulted in the indium remaining in a reduced state where it’s free to break apart more nitrates,” she added.

In previous research, the researchers discovered that gold-palladium nanoparticles were not good catalysts for breaking apart nitrates. This led to the discovery of indium and palladium as a suitable catalyst.

“Nitrates are molecules that have one nitrogen atom and three oxygen atoms,” Rice chemical engineer Michael Wong, the lead scientist on the study, said in a statement. “Nitrates turn into nitrites if they lose an oxygen, but nitrites are even more toxic than nitrates, so you don’t want to stop with nitrites. Moreover, nitrates are the more prevalent problem.

“Ultimately, the best way to remove nitrates is a catalytic process that breaks them completely apart into nitrogen and oxygen or in our case, nitrogen and water because we add a little hydrogen,” he added. “More than 75 percent of Earth’s atmosphere is gaseous nitrogen, so we’re really turning nitrates into air and water.”

Nitrates, which could also be a carcinogenic, are considered toxic to both infants and pregnant women.

Nitrate pollution is common in agricultural communities, especially in the U.S. Corn Belt and California’s Central Valley, where fertilizers are heavily used. Studies have shown that nitrate pollution is on the rise because of changing land-use patterns. 1-california-drought-farms

The Environmental Protection Agency regulates allowable limits both nitrates and nitrites for safe drinking water. In communities with polluted wells and lakes, that typically means pretreating drinking water with ion-exchange resins that trap and remove nitrates and nitrites without destroying them.

“Nitrates come mainly from agricultural runoff, which affects farming communities all over the world,” Wong said. “Nitrates are both an environmental problem and health problem because they’re toxic.

“There are ion-exchange filters that can remove them from water, but these need to be flushed every few months to reuse them, and when that happens, the flushed water just returns a concentrated dose of nitrates right back into the water supply.”

The researchers will now try to develop a commercially viable water-treatment system.

“That’s where NEWT comes in,” Wong said. “NEWT is all about taking basic science discoveries and getting them deployed in real-world conditions.

“This is going to be an example within NEWT where we have the chemistry figured out, and the next step is to create a flow system to show proof of concept that the technology can be used in the field,” he added.

The study was published in ACS Catalysis.

Rice University Study Boosts Hope for Cheaper Fuel Cells


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Rice researchers show how to optimize nanomaterials for fuel-cell cathodes

Nitrogen-doped carbon nanotubes or modified graphene nanoribbons may be suitable replacements for platinum for fast oxygen reduction, the key reaction in fuel cells that transform chemical energy into electricity, according to Rice University researchers.

The findings are from computer simulations by Rice scientists who set out to see how carbon nanomaterials can be improved for fuel-cell cathodes. Their study reveals the atom-level mechanisms by which doped nanomaterials catalyze oxygen reduction reactions (ORR).

The research appears in the Royal Society of Chemistry journal Nanoscale.

Theoretical physicist Boris Yakobson and his Rice colleagues are among many looking for a way to speed up ORR for fuel cells, which were discovered in the 19th century but not widely used until the latter part of the 20th. They have since powered transportation modes ranging from cars and buses to spacecraft.

The Rice researchers, including lead author and former postdoctoral associate Xiaolong Zou and graduate student Luqing Wang, used computer simulations to discover why graphene nanoribbons and carbon nanotubes modified with nitrogen and/or boron, long studied as a substitute for expensive platinum, are so sluggish and how they can be improved.

Doping, or chemically modifying, conductive nanotubes or nanoribbons changes their chemical bonding characteristics. They can then be used as cathodes in proton-exchange membrane fuel cells. In a simple fuel cell, anodes draw in hydrogen fuel and separate it into protons and electrons. While the negative electrons flow out as usable current, the positive protons are drawn to the cathode, where they recombine with returning electrons and oxygen to produce water.

The models showed that thinner carbon nanotubes with a relatively high concentration of nitrogen would perform best, as oxygen atoms readily bond to the carbon atom nearest the nitrogen. Nanotubes have an advantage over nanoribbons because of their curvature, which distorts chemical bonds around their circumference and leads to easier binding, the researchers found.

Rice logo_rice3The tricky bit is making a catalyst that is neither too strong nor too weak as it bonds with oxygen. The curve of the nanotube provides a way to tune the nanotubes’ binding energy, according to the researchers, who determined that “ultrathin” nanotubes with a radius between 7 and 10 angstroms would be ideal. (An angstrom is one ten-billionth of a meter; for comparison, a typical atom is about 1 angstrom in diameter.)

They also showed co-doping graphene nanoribbons with nitrogen and boron enhances the oxygen-absorbing abilities of ribbons with zigzag edges. In this case, oxygen finds a double-bonding opportunity. First, they attach directly to positively charged boron-doped sites. Second, they’re drawn by carbon atoms with high spin charge, which interacts with the oxygen atoms’ spin-polarized electron orbitals. While the spin effect enhances adsorption, the binding energy remains weak, also achieving a balance that allows for good catalytic performance.

The researchers showed the same catalytic principles held true, but to lesser effect, for nanoribbons with armchair edges.

“While doped nanotubes show good promise, the best performance can probably be achieved at the nanoribbon zigzag edges where nitrogen substitution can expose the so-called pyridinic nitrogen, which has known catalytic activity,” Yakobson said.

“If arranged in a foam-like configuration, such material can approach the efficiency of platinum,” Wang said. “If price is a consideration, it would certainly be competitive.”

Zou is now an assistant professor at Tsinghua-Berkeley Shenzhen Institute in Shenzhen City, China. Yakobson is the Karl F. Hasselmann Professor of Materials Science and NanoEngineering and a professor of chemistry.

The research was supported by the Robert Welch Foundation, the Army Research Office, the Development and Reform Commission of Shenzhen Municipality, the Youth 1000-Talent Program of China and Tsinghua-Berkeley Shenzhen Institute.

Rice – MD Anderson use Fluorescent Carbon Nanotube probes to detect ovarian cancer – Achieve first In – Vivo Success


 

 

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Abstract:
Researchers at Rice University and the University of Texas MD Anderson Cancer Center have refined and, for the first time, run in vivo tests of a method that may allow nanotube-based probes to locate specific tumors in the body. Their ability to pinpoint tumors with sub-millimeter accuracy could eventually improve early detection and treatment of ovarian cancer.

The noninvasive technique relies on single-walled carbon nanotubes that can be optically triggered to emit shortwave infrared light. The Rice lab of chemist Bruce Weisman, a pioneer in the discovery and interpretation of the phenomenon, reported the new results in the American Chemical Society journal ACS Applied Materials and Interfaces.

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For this study, the researchers used the technique to pinpoint small concentrations of nanotubes inside rodents. The lab of co-author Dr. Robert Bast Jr., an expert in ovarian cancer and vice president for translational research at MD Anderson, inserted gel-bound carbon nanotubes into the ovaries of rodents to mimic the accumulations that are expected for nanotubes linked to special antibodies that recognize tumor cells. The rodents were then scanned with the Rice lab’s custom-built optical device to detect the faint emission signatures of as little as 100 picograms of nanotubes.

The device irradiated the rodents with intense red light from an array of light-emitting diodes and read fluorescent signals with a specialized sensitive detector. Because different types of tissue absorb emissions from the nanotubes differently, the scanner took readings from many locations to triangulate the tumor’s exact location, as confirmed by later MRI scans.

Weisman said it should be possible to noninvasively find small ovarian tumors within rodents used for medical research by linking nanotubes to antibody biomarkers and administering the biomarkers intravenously. The biomarkers would accumulate at the tumor site. He said more refined versions of the optical scanner may then be able to locate a tumor within seconds, and further advances may extend the method’s application to human cancer detection. The new results suggested that antibody-nanotube probes could potentially detect tumors with as few as 100 ovarian cancer cells, which could make it a valuable tool for early detection. Rice MD Anderson Cancer CNTs 54864

Rice graduate student Ching-Wei Lin is lead author of the paper. Co-authors from the Bast group at MD Anderson are researcher Dr. Hailing Yang and senior research assistants Weiqun Mao and Lan Pang. Rice co-authors are chemistry graduate student Stephen Sanchez and Kathleen Beckingham, a professor of biosciences.

The research was supported by the National Science Foundation, the Welch Foundation, the National Institutes of Health, the John S. Dunn Foundation Collaborative Research Award Program, the National Cancer Institute, the Cancer Prevention and Research Institute of Texas, the National Foundation for Cancer Research, the Mossy Foundation, Golfers Against Cancer, the Roberson Endowment and Stuart and Gaye Lynn Zarrow.

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About Rice University
Located on a 300-acre forested campus in Houston, Rice University is consistently ranked among the nation’s top 20 universities by U.S. News & World Report. Rice has highly respected schools of Architecture, Business, Continuing Studies, Engineering, Humanities, Music, Natural Sciences and Social Sciences and is home to the Baker Institute for Public Policy.

Rice U: Nano-Shells could deliver more chemo with fewer side effects


Rice Nano shells 171108143658_1_540x360
Researchers from Rice University and Northwestern University loaded light-activated nano-shells (gold and light blue) with the anticancer drug lapatinib (yellow) by encasing the drug in an envelope of albumin (blue). Light from a near-infrared laser (center) was used to remotely trigger the release of the drug (right) after the nano-shells were taken up by cancer cells. Credit: A. Goodman/Rice University

Researchers investigating ways to deliver high doses of cancer-killing drugs inside tumors have shown they can use a laser and light-activated gold nanoparticles to remotely trigger the release of approved cancer drugs inside cancer cells in laboratory cultures.

The study by researchers at Rice University and Northwestern University Feinberg School of Medicine appears in this week’s online Early Edition of the Proceedings of the National Academy of Sciences. It employed gold nanoshells to deliver toxic doses of two drugs — lapatinib and docetaxel — inside breast cancer cells. The researchers showed they could use a laser to remotely trigger the particles to release the drugs after they entered the cells.

Though the tests were conducted with cell cultures in a lab, the research was designed to demonstrate clinical applicability: The nanoparticles are nontoxic, the drugs are widely used and the low-power, infrared laser can noninvasively shine through tissue and reach tumors several inches below the skin.

“In future studies, we plan to use a Trojan-horse strategy to get the drug-laden nanoshells inside tumors,” said Naomi Halas, an engineer, chemist and physicist at Rice University who invented gold nanoshells and has spent more than 15 years researching their anticancer potential. “Macrophages, a type of white blood cell that’s been shown to penetrate tumors, will carry the drug-particle complexes into tumors, and once there we use a laser to release the drugs.”

Co-author Susan Clare, a research associate professor of surgery at the Northwestern University Feinberg School of Medicine, said the PNAS study was designed to demonstrate the feasibility of the Trojan-horse approach. In addition to demonstrating that drugs could be released inside cancer cells, the study also showed that in macrophages, the drugs did not detach prior to triggering.

“Getting chemotherapeutic drugs to penetrate tumors is very challenging,” said Clare, also a Northwestern Medicine breast cancer surgeon. “Drugs tend to get pushed out of tumors rather than drawn in. To get an effective dose at the tumor, patients often have to take so much of the drug that nausea and other side effects become severe. Our hope is that the combination of macrophages and triggered drug-release will boost the effective dose of drugs within tumors so that patients can take less rather than more.”

If the approach works, Clare said, it could result in fewer side effects and potentially be used to treat many kinds of cancer. For example, one of the drugs in the study, lapatinib, is part of a broad class of chemotherapies called tyrosine kinase inhibitors that target specific proteins linked to different types of cancer. Other Federal Drug Administration-approved drugs in the class include imatinib (leukemia), gefitinib (breast, lung), erlotinib (lung, pancreatic), sunitinib (stomach, kidney) and sorafenib (liver, thyroid and kidney).

“All the tyrosine kinase inhibitors are notoriously insoluble in water,” said Amanda Goodman, a Rice alumna and lead author of the PNAS study. “As a drug class, they have poor bioavailability, which means that a relatively small proportion of the drug in each pill is actually killing cancer cells. If our method works for lapatinib and breast cancer, it may also work for the other drugs in the class.”

Halas invented nanoshells at Rice in the 1990s. About 20 times smaller than a red blood cell, they are made of a sphere of glass covered by a thin layer of gold. Nanoshells can be tuned to capture energy from specific wavelengths of light, including near-infrared (near-IR), a nonvisible wavelength that passes through most tissues in the body. Nanospectra Biosciences, a licensee of this technology, has performed several clinical trials over the past decade using nanoshells as photothermal agents that destroy tumors with infrared light.

Clare and Halas’ collaboration on nanoshell-based drug delivery began more than 10 years ago. In earlier work, they showed that a near-IR continuous-wave laser — the same kind that produces heat in the photothermal applications of nanoshells — could be used to trigger the release of drugs from nanoshells.

In the latest study, Goodman contrasted the use of continuous-wave laser triggering and triggering with a low-power pulse laser. Using each type of laser, she demonstrated the remotely triggered release of drugs from two types of nanoshell-drug conjugates. One type used a DNA linker and the drug docetaxel, and the other employed a coating of the blood protein albumin to trap and hold lapatinib. In each case, Goodman found she could trigger the release of the drug after the nanoshells were taken up inside cancer cells. She also found no measureable premature release of drugs in macrophages in either case.

Halas and Clare said they hope to begin animal tests of the technology soon and have an established mouse model that could be used for the testing.

“I’m particularly excited about the potential for lapatinib,” Clare said. “The first time I heard about Naomi’s work, I wondered if it might be the answer to delivering drugs into the anoxic (depleted of oxygen) interior of tumors where some of the most aggressive cancer cells lurk. As clinicians, we’re always looking for ways to keep cancer from coming back months or years later, and I am hopeful this can do that.”

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Materials provided by Rice UniversityNote: Content may be edited for style and length.

Rice U: Long Nanotube fibers for use in Large-Scale Aerospace, Consumer Electronics and Textile Applications


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Rice University researchers advance characterization, purification of Nanotube wires and films

RICE UNIVERSITY

To make continuous, strong and conductive carbon nanotube fibers, it’s best to start with long nanotubes, according to scientists at Rice University.

The Rice lab of chemist and chemical engineer Matteo Pasquali, which demonstrated its pioneering method to spin carbon nanotube into fibers in 2013, has advanced the art of making nanotube-based materials with two new papers in the American Chemical Society’s ACS Applied Materials and Interfaces.

The first paper characterized 19 batches of nanotubes produced by as many manufacturers to determine which nanotube characteristics yield the most conductive and strongest fibers for use in large-scale aerospace, consumer electronics and textile applications.

The researchers determined the nanotubes’ aspect ratio — length versus width — is a critical factor, as is the overall purity of the batch. They found the tubes’ diameters, number of walls and crystalline quality are not as important to the product properties.

Pasquali said that while the aspect ratio of nanotubes was known to have an influence on fiber properties, this is the first systematic work to establish the relationship across a broad range of nanotube samples. Researchers found that longer nanotubes could be processed as well as shorter ones, and that mechanical strength and electrical conductivity increased in lockstep.Rice II nanotubes

The best fibers had an average tensile strength of 2.4 gigapascals (GPa) and electrical conductivity of 8.5 megasiemens per meter, about 15 percent of the conductivity of copper. Increasing nanotube length during synthesis will provide a path toward further property improvements, Pasquali said.

The second paper focused on purifying fibers produced by the floating catalyst method for use in films and aerogels. This process is fast, efficient and cost-effective on a medium scale and can yield the direct spinning of high-quality nanotube fibers; however, it leaves behind impurities, including metallic catalyst particles and bits of leftover carbon, allows less control of fiber structure and limits opportunities to scale up, Pasquali said.

“That’s where these two papers converge,” he said. “There are basically two ways to make nanotube fibers. In one, you make the nanotubes and then you spin them into fibers, which is what we’ve developed at Rice. In the other, developed at the University of Cambridge, you make nanotubes in a reactor and tune the reactor such that, at the end, you can pull the nanotubes out directly as fibers.

“It’s clear those direct-spun fibers include longer nanotubes, so there’s an interest in getting the tubes included in those fibers as a source of material for our spinning method,” Pasquali said. “This work is a first step toward that goal.”

Q Flow MODEL-OF-CARBON-NANOTUBE-PAIDThe reactor process developed a decade ago by materials scientist Alan Windle at the University of Cambridge produces the requisite long nanotubes and fibers in one step, but the fibers must be purified, Pasquali said. Researchers at Rice and the National University of Singapore (NUS) have developed a simple oxidative method to clean the fibers and make them usable for a broader range of applications.

The labs purified fiber samples in an oven, first burning out carbon impurities in air at 500 degrees Celsius (932 degrees Fahrenheit) and then immersing them in hydrochloric acid to dissolve iron catalyst impurities.

Impurities in the resulting fibers were reduced to 5 percent of the material, which made them soluble in acids. The researchers then used the nanotube solution to make conductive, transparent thin films.

“There is great potential for these disparate techniques to be combined to produce superior fibers and the technology scaled up for industrial use,” said co-author Hai Minh Duong, an NUS assistant professor of mechanical engineering. “The floating catalyst method can produce various types of nanotubes with good morphology control fairly quickly. The nanotube filaments can be collected directly from their aerogel formed in the reactor. These nanotube filaments can then be purified and twisted into fibers using the wetting technique developed by the Pasquali group.”

Pasquali noted the collaboration between Rice and Singapore represents convergence of another kind. “This may well be the first time someone from the Cambridge fiber spinning line (Duong was a postdoctoral researcher in Windle’s lab) and the Rice fiber spinning line have converged,” he said. “We’re working together to try out materials made in the Cambridge process and adapting them to the Rice process.”

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Alumnus Dmitri Tsentalovich, currently an academic visitor at Rice, is lead author of the characterization paper. Co-authors are graduate students Robert Headrick and Colin Young, research scientist Francesca Mirri and alumni Junli Hao and Natnael Behabtu, all of Rice.

Thang Tran of Rice and NUS and Headrick are co-lead authors of the catalyst paper. Co-authors are graduate student Amram Bengio and research specialist Vida Jamali, both of Rice, and research scientist Sandar Myo and graduate student Hamed Khoshnevis, both of NUS.

The Air Force Office of Scientific Research, the Welch Foundation and NASA supported both projects. The characterization project received additional support from the Department of Energy. The catalyst project received additional support from the Temasek Laboratory in Singapore.

Influence of Carbon Nanotube Characteristics on Macroscopic Fiber Properties: http://pubs.acs.org/doi/abs/10.1021/acsami.7b10968

Purification and Dissolution of Carbon Nanotube Fibers Spun from Floating Catalyst Method: http://pubs.acs.org/doi/abs/10.1021/acsami.7b09287

This news release can be found online at http://news.rice.edu/2017/10/15/long-nanotubes-make-strong-fibers/

1-blind CNTWhat Are Carbon Nanotubes and What are some of their Applications

Carbon nanotubes (CNTs) are allotropes of carbon with a cylindrical nanostructure.

 

 

 

These cylindrical carbonmolecules have unusual properties, which are valuable for nanotechnologyelectronicsoptics and other fields of materials science and technology. Owing to the material’s exceptional strength and stiffness, nanotubes have been constructed with length-to-diameter ratio of up to 132,000,000:1,[1] significantly larger than for any other material.

In addition, owing to their extraordinary thermal conductivity, mechanical, and electrical properties, carbon nanotubes find applications as additives to various structural materials. For instance, nanotubes form a tiny portion of the material(s) in some (primarily carbon fiber) baseball bats, golf clubs, car parts or damascus steel.

 

Rice University (NEWT) / China team use phage-enhanced nanoparticles to kill bacteria that foul water treatment systems


Clusters of nanoparticles with phage viruses attached find and kill Escherichia coli bacteria in a lab test at Rice University. 

Abstract:
Magnetic nanoparticle clusters have the power to punch through biofilms to reach bacteria that can foul water treatment systems, according to scientists at Rice University and the University of Science and Technology of China.
Magnetized viruses attack harmful bacteria: Rice, China team uses phage-enhanced nanoparticles to kill bacteria that foul water treatment systems.

Researchers at Rice and the University of Science and Technology of China have developed a combination of antibacterial phages and magnetic nanoparticle clusters that infect and destroy bacteria that are usually protected by biofilms in water treatment systems. (Credit: Alvarez Group/Rice University)

The nanoclusters developed through Rice’s Nanotechnology-Enabled Water Treatment (NEWT) Engineering Research Center carry bacteriophages – viruses that infect and propagate in bacteria – and deliver them to targets that generally resist chemical disinfection.

Without the pull of a magnetic host, these “phages” disperse in solution, largely fail to penetrate biofilms and allow bacteria to grow in solution and even corrode metal, a costly problem for water distribution systems.

The Rice lab of environmental engineer Pedro Alvarez and colleagues in China developed and tested clusters that immobilize the phages. A weak magnetic field draws them into biofilms to their targets.

The research is detailed in the Royal Society of Chemistry’s Environmental Science: Nano.
“This novel approach, which arises from the convergence of nanotechnology and virology, has a great potential to treat difficult-to-eradicate biofilms in an effective manner that does not generate harmful disinfection byproducts,” Alvarez said.

Biofilms can be beneficial in some wastewater treatment or industrial fermentation reactors owing to their enhanced reaction rates and resistance to exogenous stresses, said Rice graduate student and co-lead author Pingfeng Yu. “However, biofilms can be very harmful in water distribution and storage systems since they can shelter pathogenic microorganisms that pose significant public health concerns and may also contribute to corrosion and associated economic losses,” he said.

The lab used phages that are polyvalent – able to attack more than one type of bacteria – to target lab-grown films that contained strains of Escherichia coli associated with infectious diseases and Pseudomonas aeruginosa, which is prone to antibiotic resistance.

The phages were combined with nanoclusters of carbon, sulfur and iron oxide that were further modified with amino groups. The amino coating prompted the phages to bond with the clusters head-first, which left their infectious tails exposed and able to infect bacteria.

The researchers used a relatively weak magnetic field to push the nanoclusters into the film and disrupt it. Images showed they effectively killed E. coli and P. aeruginosa over around 90 percent of the film in a test 96-well plate versus less than 40 percent in a plate with phages alone.

The researchers noted bacteria may still develop resistance to phages, but the ability to quickly disrupt biofilms would make that more difficult. Alvarez said the lab is working on phage “cocktails” that would combine multiple types of phages and/or antibiotics with the particles to inhibit resistance.

Graduate student Ling-Li Li of the University of Science and Technology of China, Hefei, is co-lead author of the paper. Co-authors are graduate student Sheng-Song Yu and Han-Qing Yu, a professor at the University of Science and Technology of China, and graduate student Xifan Wang and temporary research scientist Jacques Mathieu of Rice.


The National Science Foundation and its Rice-based NEWT Engineering Research Center supported the research.

Rice University: Designing Materials with ‘Stiffness and Flexibility’


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Materials scientists at Rice University are looking to nature — at the discs in human spines and the skin in ocean-diving fish, for example — for clues about designing materials with seemingly contradictory properties — flexibility and stiffness.

In research graduate student Peter Owuor, research scientist Chandra Sekhar Tiwary and colleagues from the laboratories of Rice Professor Pulickel Ajayan and Jun Lou found they could increase the stiffness, or “elastic modulus,” of a soft silicon-based polymer by infusing it with tiny pockets of liquid gallium.

Such composites could find use in high-energy absorption materials and shock absorbers and in biomimetic structures like artificial intervertebral discs, they said.

Owuor said conventional wisdom in composite design for the past 60 years has been that adding a harder substance increases modulus and adding a softer one decreases modulus. In most instances, that’s correct.

“People had not really looked at it from the other way around,” he said. “Is it possible to add something soft inside something else that is also soft and get something that has a higher modulus? If you look at the natural world, there are plenty of examples where you find exactly that. As materials scientists, we wanted to study this, not from a biological perspective but rather from a mechanical one.”

For example, the discs between the vertebrae in human spines, which act like both shock absorbers and ligaments, are made of a tough outer layer of cartilage and a soft, jelly-like interior. And the outer skin of deep-diving ocean fish and mammals contain myriad tiny oil-filled chambers — some no larger than a virus and others larger than entire cells — that allow the animals to withstand the intense pressures that exist thousands of feet below the ocean’s surface.Rice Flex Materials2 38906-53.jpg

Choosing the basic materials to model these living systems was relatively easy, but finding a way to bring them together to mimic nature proved difficult, said Tiwary, a postdoctoral research associate in Rice’s Department of Materials Science and NanoEngineering.

Polydimethylsiloxane, or PDMS, was chosen as the soft encapsulating layer for a number of reasons: It’s cheap, inert, nontoxic and widely used in everything from caulk and aquarium sealants to cosmetics and food additives. It also dries clear, which made it easy to see the bubbles of liquid the team wanted to encapsulate. For that, the researchers chose gallium, which like mercury is liquid at room temperature, but unlike mercury is nontoxic and relatively easy to work with.

Owuor said it took nearly four months to find a recipe for encapsulating bubbles of gallium inside PDMS. His test samples are about the diameter of a small coin and as much as a quarter-inch thick. By curing the PDMS slowly, Owuor developed a process by which he could add gallium droplets of various sizes. Some samples contained one large inner chamber, and others contained up to a dozen discrete droplets.

Each sample was subjected to dozens of tests. A dynamic mechanical analysis instrument was used to measure how much the material deformed under load, and various measures like stiffness, toughness and elasticity were measured under a variety of conditions. For example, with a relatively small amount of cooling, gallium can be turned into a solid. So the team was able to compare some measurements taken when the gallium spheres were liquid with measures taken when the spheres were solid.

Collaborators Roy Mahapatra and Shashishekarayya Hiremath of the Indian Institute of Science at Bangalore used finite element modeling and hydrodynamic simulations to help the team analyze how the materials behaved under mechanical stress. Based on this, the researchers determined that pockets of liquid gallium gave the composite higher energy absorption and dissipation characteristics than plain PDMS or PDMS with air-filled pockets.

“What we’ve shown is that putting liquid inside a solid is not always going to make it softer, and thanks to our collaborators we are able to explain why this is the case,” Tiwary said. “Next we hope to use this understanding to try to engineer materials to take advantage of these properties.”

Owuor and Tiwary said just using nanoengineering alone may not provide a maximum effect. Instead, nature employs hierarchical structures with features of varying sizes that repeat at larger scales, like those found in the oil-filled chambers in fish skin.

“If you look at (the fish’s) membrane and you section it, there is a layer where you have spheres with big diameters, and as you move, the diameters keep decreasing,” Owuor said. “The chambers are seen across the whole scale, from the nano- all the way out to the microscale.

Tiwary said, “There are important nanoscale features in nature, but it’s not all nano. We may find that engineering at the nanoscale alone isn’t enough. We want to see if we can start designing in a hierarchical way.”

Ajayan is chair of Rice’s Department of Materials Science and NanoEngineering, the Benjamin M. and Mary Greenwood Anderson Professor in Engineering and a professor of chemistry.

The research was supported by the Air Force Office of Scientific Research. Additional Rice co-authors include Lou, Alin Chipara and Robert Vajtai.

Rice U Researchers Create 3-D printed Graphene Foam (Ultra-Thin Graphene) + New Video for ‘Graphene Nano-Tubes’ ~ Supports New Li-Io Battery Technology


3D Graphene

Researchers from Rice University and China’s Tianjin University have used 3-D laser printing to fabricate centimeter-sized objects of atomically thin graphene.

The research could yield industrially useful quantities of bulk graphene and is described online in a new study in the American Chemical Society journal ACS Nano.

“This study is a first of its kind,” said Rice chemist James Tour, co-corresponding author of the paper. “We have shown how to make 3-D graphene foams from nongraphene starting materials, and the method lends itself to being scaled to graphene foams for additive manufacturing applications with pore-size control.”

Graphene, one of the most intensely studied nanomaterials of the decade, is a two-dimensional sheet of pure carbon that is both ultrastrong and conductive. Scientists hope to use graphene for everything from nanoelectronics and aircraft de-icers to batteries and bone implants. But most industrial applications would require bulk quantities of graphene in a three-dimensional form, and scientists have struggled to find simple ways of creating bulk 3-D graphene.

For example, researchers in Tour’s lab began using lasers, powdered sugar and nickel to make 3-D graphene foam in late 2016. Earlier this year they showed that they could reinforce the foam with carbon nanotubes, which produced a material they dubbed “rebar graphene” that could retain its shape while supporting 3,000 times its own weight. But making rebar graphene was no simple task. It required a pre-fabricated 3-D mold, a 1,000-degree Celsius chemical vapor deposition (CVD) process and nearly three hours of heating and cooling.

In the latest study, a team from Tour’s lab and the labs of Rice’s Jun Luo and Tianjin’s Naiqin Zhao adapted a common 3-D printing technique to make fingertip-size blocks of graphene foam. The process is conducted at room temperature. No molds are required and the starting materials are powdered sugar and nickel powder.

“This simple and efficient method does away with the need for both cold-press molds and high-temperature CVD treatment,” said co-lead author Junwei Sha, a former student in Tour’s lab who is now a postdoctoral researcher at Tianjin. “We should also be able to use this process to produce specific types of graphene foam like 3-D printed rebar graphene as well as both nitrogen- and sulfur-doped graphene foam by changing the precursor powders.”

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3-D graphene foam objects are produced by shining a laser on a mixture of powdered sugar and nickel powder. The laser is moved back and forth to melt sugar in a 2-D pattern, and nickel acts as a catalyst to spur the growth of graphene foam. The process is repeated with successive layers of powder to build up 3-D objects. (Image courtesy of Tour Group/Rice University)

Three-D laser printers work differently than the more familiar extrusion-based 3-D printers, which create objects by squeezing melted plastic through a needle as they trace out two-dimensional patterns. In 3-D laser sintering, a laser shines down onto a flat bed of powder. Wherever the laser touches powder, it melts or sinters the powder into a solid form. The laser is rastered, or moved back and forth, line by line to create a single two-dimensional slice of a larger object. Then a new layer of powder is laid over the top of that layer and the process is repeated to build up three-dimensional objects from successive two-dimensional layers.

The new Rice process used a commercially available CO2 laser. When this laser was shone onto the sugar and nickel powder, the sugar was melted and the nickel acted as a catalyst. Graphene formed as the mixture cooled after the laser had moved on to melt sugar in the next spot, and Sha and colleagues conducted an exhaustive study to find the optimal amount of time and laser power to maximize graphene production.

The foam created by the process is a low-density, 3-D form of graphene with large pores that account for more than 99 percent of its volume.

“The 3-D graphene foams prepared by our method show promise for applications that require rapid prototyping and manufacturing of 3-D carbon materials, including energy storage, damping and sound absorption,” said co-lead author Yilun Li, a graduate student at Rice.

Read More: Video

Graphene foam reinforced with carbon nanotubes can hold thousands of times its own weight and still bounce back to its full height, according to Rice University scientists. The material is thermally stable and highly conductive, making it suitable for batteries and other electrical applications. Read about it at http://news.rice.edu/2017/02/13/graph…

Rice U: New Lithium metal battery prototype boasts 3X the capacity of current lithium-ions ~ Dendrite Problem Solved?


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Could a new material involving a carbon nanotube and graphene hybrid put an end to the dendrite problem in lithium batteries? (Credit: Tour Group/Rice University)

The high energy capacity of lithium-ion batteries has led to them powering everything from tiny mobile devices to huge trucks. But current lithium-ion battery technology is nearing its limits and the search is on for a better lithium battery. But one thing stands in the way: dendrites. If a new technology by Rice University scientists lives up to its potential, it could solve this problem and enable lithium-metal batteries that can hold three times the energy of lithium-ion ones.

Dendrites are microscopic lithium fibers that form on the anodes during the charging process, spreading like a rash till they reach the other electrode and causing the battery to short circuit. As companies such as Samsung know only too well, this can cause the battery to catch fire or even explode.

“Lithium-ion batteries have changed the world, no doubt,” says chemist Dr. James Tour, who led the study. “But they’re about as good as they’re going to get. Your cellphone’s battery won’t last any longer until new technology comes along.”

Rice logo_rice3So until scientists can figure out a way to solve the problem of dendrites, we’ll have to put our hopes for a higher capacity, faster-charging battery that can quell range anxiety on hold. This explains why there’s been no shortage of attempts to solve this problem, from using Kevlar to slow down dendrite growth to creating a new electrolyte that could lead to the development of an anode-free cell. So how does this new technology from Rice University compare?

For a start, it’s able to stop dendrite growth in its tracks. Key to it is a unique anode made from a material that was first created at the university five years ago. By using a covalent bond structure, it combines a two-dimensional graphene sheet and carbon nanotubes to form a seamless three-dimensional structure. As Tour explained back when the material was first unveiled:

“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.”

Close-up of the lithium metal coating the graphene-nanotube anode (Credit: Tour Group/Rice University)

 

Envisioned for use in energy storage and electronics applications such as supercapacitors, it wasn’t until 2014, when co-lead author Abdul-Rahman Raji was experimenting with lithium metal and the graphene-nanotube hybrid, that the researchers discovered its potential as a dendrite inhibitor.

“I reasoned that lithium metal must have plated on the electrode while analyzing results of experiments carried out to store lithium ions in the anode material combined with a lithium cobalt oxide cathode in a full cell,” says Raji. “We were excited because the voltage profile of the full cell was very flat. At that moment, we knew we had found something special.”

Closer analysis revealed no dendrites had grown when the lithium metal was deposited into a standalone hybrid anode – but would it work in a proper battery?

To test the anode, the researchers built full battery prototypes with sulfur-based cathodes that retained 80 percent capacity after more than 500 charge-discharge cycles (i.e. the rough equivalent of what a cellphone goes through in a two-year period). No signs of dendrites were observed on the anodes.

How it works

The low density and high surface area of the nanotube forest allow the lithium metal to coat the carbon hybrid material evenly when the battery is charged. And since there is plenty of space for the particles to slip in and out during the charge and discharge cycle, they end up being evenly distributed and this stops the growth of dendrites altogether.

According to the study, the anode material is capable of a lithium storage capacity of 3,351 milliamp hours per gram, which is close to pure lithium’s theoretical maximum of 3,860 milliamp hours per gram, and 10 times that of lithium-ion batteries. And since the nanotube carpet has a low density, this means it’s able to coat all the way down to substrate and maximize use of the available volume.

“Many people doing battery research only make the anode, because to do the whole package is much harder,” says Tour. “We had to develop a commensurate cathode technology based upon sulfur to accommodate these ultrahigh-capacity lithium anodes in first-generation systems. We’re producing these full batteries, cathode plus anode, on a pilot scale, and they’re being tested.”

The study was published in ACS Nano.

Source: Rice University