25 Mar 2016
“This microbial nanowire is made of but a single peptide subunit,” said Gemma Reguera, lead author and MSU microbiologist. “Being made of protein, these organic nanowires are biodegradable and biocompatible. This discovery thus opens many applications in nanoelectronics such as the development of medical sensors and electronic devices that can be interfaced with human tissues.”
Since existing nanotechnologies incorporate exotic metals into their designs, the cost of organic nanowires is much more cost effective as well, she added.
How the nanowires function in nature is comparable to breathing. Bacterial cells, like humans, have to breathe. The process of respiration involves moving electrons out of an organism. Geobacter bacteria use the protein nanowires to bind and breathe metal-containing minerals such as iron oxides and soluble toxic metals such as uranium. The toxins are mineralized on the nanowires’ surface, preventing the metals from permeating the cell.
Reguera’s team purified their protein fibers, which are about 2 nanometers in diameter. Using the same toolset of nanotechnologists, the scientists were able to measure the high velocities at which the proteins were passing electrons.
“They are like power lines at the nanoscale,” Reguera said. “This also is the first study to show the ability of electrons to travel such long distances — more than a 1,000 times what’s been previously proven — along proteins.”
The researchers also identified metal traps on the surface of the protein nanowires that bind uranium with great affinity and could potentially trap other metals. These findings could provide the basis for systems that integrate protein nanowires to mine gold and other precious metals, scrubbers that can be deployed to immobilize uranium at remediation sites and more.
Reguera’s nanowires also can be modified to seek out other materials in which to help them breathe.
“The Geobacter cells are making these protein fibers naturally to breathe certain metals. We can use genetic engineering to tune the electronic and biochemical properties of the nanowires and enable new functionalities. We also can mimic the natural manufacturing process in the lab to mass-produce them in inexpensive and environmentally friendly processes,” Reguera said. “This contrasts dramatically with the manufacturing of humanmade inorganic nanowires, which involve high temperatures, toxic solvents, vacuums and specialized equipment.”
This discovery came from truly listening to bacteria, Reguera said.
“The protein is getting the credit, but we can’t forget to thank the bacteria that invented this,” she said. “It’s always wise to go back and ask bacteria what else they can teach us. In a way, we are eavesdropping on microbial conversations. It’s like listening to our elders, learning from their wisdom and taking it further.”
- Sanela Lampa-Pastirk, Joshua P. Veazey, Kathleen A. Walsh, Gustavo T. Feliciano, Rebecca J. Steidl, Stuart H. Tessmer, Gemma Reguera. Thermally activated charge transport in microbial protein nanowires. Scientific Reports, 2016; 6: 23517 DOI: 10.1038/srep23517
With that in mind, researchers at Case Western Reserve University have developed flexible wire-shaped microsupercapacitors that can be woven into a jacket, shirt or dress.
By their design or by connecting the capacitors in series or parallel, the devices can be tailored to match the charge storage and delivery needs of electronics donned.
While there’s been progress in development of those electronics–body cameras, smart glasses, sensors that monitor health, activity trackers and more–one challenge remaining is providing less obtrusive and cumbersome power sources.
“The area of clothing is fixed, so to generate the power density needed in a small area, we grew radially-aligned titanium oxide nanotubes on a titanium wire used as the main electrode,” said Liming Dai, the Kent Hale Smith Professor of Macromolecular Science and Engineering. “By increasing the surface area of the electrode, you increase the capacitance.”
Dai and Tao Chen, a postdoctoral fellow in molecular science and engineering at Case Western Reserve, published their research on the microsupercapacitor in the journal Energy Storage Materials this week. The study builds on earlier carbon-based supercapacitors.
A capacitor is cousin to the battery, but offers the advantage of charging and releasing energy much faster.
How it works
In this new supercapacitor, the modified titanium wire is coated with a solid electrolyte made of polyvinyl alcohol and phosphoric acid. The wire is then wrapped with either yarn or a sheet made of aligned carbon nanotubes, which serves as the second electrode. The titanium oxide nanotubes, which are semiconducting, separate the two active portions of the electrodes, preventing a short circuit.
In testing, capacitance–the capability to store charge–increased from 0.57 to 0.9 to 1.04 milliFarads per micrometer as the strands of carbon nanotube yarn were increased from 1 to 2 to 3.
When wrapped with a sheet of carbon nanotubes, which increases the effective area of electrode, the microsupercapactitor stored 1.84 milliFarads per micrometer. Energy density was 0.16 x 10-3 milliwatt-hours per cubic centimeter and power density .01 milliwatt per cubic centimeter.
Whether wrapped with yarn or a sheet, the microsupercapacitor retained at least 80 percent of its capacitance after 1,000 charge-discharge cycles. To match various specific power needs of wearable devices, the wire-shaped capacitors can be connected in series or parallel to raise voltage or current, the researchers say.
When bent up to 180 degrees hundreds of times, the capacitors showed no loss of performance. Those wrapped in sheets showed more mechanical strength.
“They’re very flexible, so they can be integrated into fabric or textile materials,” Dai said. “They can be a wearable, flexible power source for wearable electronics and also for self-powered biosensors or other biomedical devices, particularly for applications inside the body.”
Dai ‘s lab is in the process of weaving the wire-like capacitors into fabric and integrating them with a wearable device.
- Tao Chen, Liming Dai. Flexible and wearable wire-shaped microsupercapacitors based on highly aligned titania and carbon nanotubes. Energy Storage Materials, 2016; 2: 21 DOI: 10.1016/j.ensm.2015.11.004
A team of researchers working in China has found a way to dramatically improve the energy storage capacity of supercapacitors—by doping carbon tubes with nitrogen. In their paper published in the journal Science, the team describes their process and how well the newly developed supercapacitors worked, and their goal of one day helping supercapacitors compete with batteries.
Like a battery, a capacitor is able to hold a charge, unlike a battery, however, it is able to be charged and discharged very quickly—the down side to capacitors is that they cannot hold nearly as much charge per kilogram as batteries. The work by the team in China is a step towards increasing the amount of charge that can be held by supercapacitors (capacitors that have much higher capacitance than standard capacitors—they generally employ carbon-based electrodes)—in this case, they report a threefold increase using their new method—noting also that that their supercapacitor was capable of storing 41 watt-hours per kilogram and could deliver 26 kilowatts per kilogram to a device.
The new supercapacitor was made by first forming a template made of tubes of silica. The team then covered the inside of the tubes with carbon using chemical vapor deposition and then etched away the silica, leaving just the carbon tubes, each approximately 4 to 6 nanometers in length. Then, the carbon tubes were doped with nitrogen atoms. Electrodes were made from the resulting material by pressing it in powder form into a graphene foam. The researchers report that the doping aided in chemical reactions within the supercapacitor without causing any changes to its electrical conductivity, which meant that it was still able to charge and discharge as quickly as conventional supercapcitors. The only difference was the dramatically increased storage capacity.
Because of the huge increase in storage capacity, the team believes they are on the path to building a supercapacitor able to compete directly with batteries, perhaps even lithium-ion batteries. They note that would mean being able to charge a phone in mere seconds. But before that can happen, the team is looking to industrialize their current new supercapacitor, to allow for its use in actual devices.
More information: T. Lin et al. Nitrogen-doped mesoporous carbon of extraordinary capacitance for electrochemical energy storage, Science (2015). DOI: 10.1126/science.aab3798
Carbon-based supercapacitors can provide high electrical power, but they do not have sufficient energy density to directly compete with batteries. We found that a nitrogen-doped ordered mesoporous few-layer carbon has a capacitance of 855 farads per gram in aqueous electrolytes and can be bipolarly charged or discharged at a fast, carbon-like speed. The improvement mostly stems from robust redox reactions at nitrogen-associated defects that transform inert graphene-like layered carbon into an electrochemically active substance without affecting its electric conductivity. These bipolar aqueous-electrolyte electrochemical cells offer power densities and lifetimes similar to those of carbon-based supercapacitors and can store a specific energy of 41 watt-hours per kilogram (19.5 watt-hours per liter).
OAK RIDGE, Tenn., July 22, 2015—Semiconductors, metals and insulators must be integrated to make the transistors that are the electronic building blocks of your smartphone, computer and other microchip-enabled devices. Today’s transistors are miniscule—a mere 10 nanometers wide—and formed from three-dimensional (3D) crystals.
But a disruptive new technology looms that uses two-dimensional (2D) crystals, just 1 nanometer thick, to enable ultrathin electronics. Scientists worldwide are investigating 2D crystals made from common layered materials to constrain electron transport within just two dimensions. Researchers had previously found ways to lithographically pattern single layers of carbon atoms called graphene into ribbon-like “wires” complete with insulation provided by a similar layer of boron nitride. But until now they have lacked synthesis and processing methods to lithographically pattern junctions between two different semiconductors within a single nanometer-thick layer to form transistors, the building blocks of ultrathin electronic devices.
Now for the first time, researchers at the Department of Energy’s Oak Ridge National Laboratory have combined a novel synthesis process with commercial electron-beam lithography techniques to produce arrays of semiconductor junctions in arbitrary patterns within a single, nanometer-thick semiconductor crystal. The process relies upon transforming patterned regions of one existing, single-layer crystal into another. The researchers first grew single, nanometer-thick layers of molybdenum diselenide crystals on substrates and then deposited protective patterns of silicon oxide using standard lithography techniques. Then they bombarded the exposed regions of the crystals with a laser-generated beam of sulfur atoms. The sulfur atoms replaced the selenium atoms in the crystals to form molybdenum disulfide, which has a nearly identical crystal structure. The two semiconductor crystals formed sharp junctions, the desired building blocks of electronics. Nature Communications reports the accomplishment.
“We can literally make any kind of pattern that we want,” said Masoud Mahjouri-Samani, who co-led the study with David Geohegan. Geohegan, head of ORNL’s Nanomaterials Synthesis and Functional Assembly Group at the Center for Nanophase Materials Sciences, is the principal investigator of a Department of Energy basic science project focusing on the growth mechanisms and controlled synthesis of nanomaterials. Millions of 2D building blocks with numerous patterns may be made concurrently, Mahjouri-Samani added. In the future, it might be possible to produce different patterns on the top and bottom of a sheet. Further complexity could be introduced by layering sheets with different patterns.
Added Geohegan, “The development of a scalable, easily implemented process to lithographically pattern and easily form lateral semiconducting heterojunctions within two-dimensional crystals fulfills a critical need for ‘building blocks’ to enable next-generation ultrathin devices for applications ranging from flexible consumer electronics to solar energy.”
Tuning the bandgap
“We chose pulsed laser deposition of sulfur because of the digital control it gives you over the flux of the material that comes to the surface,” said Mahjouri-Samani. “You can basically make any kind of intermediate alloy. You can just replace, say, 20 percent of the selenium with sulfur, or 30 percent, or 50 percent.” Added Geohegan, “Pulsed laser deposition also lets the kinetic energy of the sulfur atoms be tuned, allowing you to explore a wider range of processing conditions.”
It is important that by controlling the ratio of sulfur to selenium within the crystal, the researchers can tune the bandgap of the semiconductors, an attribute that determines electronic and optical properties. To make optoelectronic devices such as electroluminescent displays, microchip fabricators integrate semiconductors with different bandgaps. For example, molybdenum disulfide’s bandgap is greater than molybdenum diselenide’s. Applying voltage to a crystal containing both semiconductors causes electrons and “holes” (positive charges created when electrons vacate) to move from molybdenum disulfide into molybdenum diselenide and recombine to emit light at the bandgap of molybdenum diselenide. For that reason, engineering the bandgaps of monolayer systems can allow the generation of light with many different colors, as well as enable other applications such as transistors and sensors, Mahjouri-Samani said.
Next the researchers will see if their pulsed laser vaporization and conversion method will work with atoms other than sulfur and selenium. “We’re trying to make more complex systems in a 2D plane—integrate more ingredients, put in different building blocks—because at the end of the day, a complete working device needs different semiconductors and metals and insulators,” Mahjouri-Samani said.
To understand the process of converting one nanometer-thick crystal into another, the researchers used powerful electron microscopy capabilities available at ORNL, notably atomic-resolution Z-contrast scanning transmission electron microscopy, which was developed at the lab and is now available to scientists worldwide using the Center for Nanophase Materials Sciences. Employing this technique, electron microscopists Andrew Lupini and visiting scientist Leonardo Basile imaged hexagonal networks of individual columns of atoms in the nanometer-thick molybdenum diselenide and molybdenum disulfide crystals.
“We could directly distinguish between sulfur and selenium atoms by their intensities in the image,” Lupini said. “These images and electron energy loss spectroscopy allowed the team to characterize the semiconductor heterojunction with atomic precision.”
The title of the paper is “Patterned Arrays of Lateral Heterojunctions within Monolayer Two-Dimensional Semiconductors.”
The research was sponsored by the U.S. Department of Energy, Office of Science. A portion of the work was conducted at the Center for Nanophase Materials Sciences, a DOE Office of Science User Facility at ORNL. Basile received support from the National Secretariat of Higher Education, Science, Technology and Innovation of Ecuador.
UT-Battelle manages ORNL for DOE’s Office of Science. The single largest supporter of basic research in the physical sciences in the United States, the Office of Science is working to address some of the most pressing challenges of our time.