Category Archives: energy

Using light to make gold crystal nanoparticles

Gold crystal nanoparticles? Courtesy: University of Florida

Gold crystal nanoparticles? Courtesy: University of Florida

A team from the University of Florida has used gold instead of silver in a process known as plasmon-driven synthesis. From a July 8, 2016 news item on phys.org,

A team of University of Florida researchers has figured out how gold can be used in crystals grown by light to create nanoparticles, a discovery that has major implications for industry and cancer treatment and could improve the function of pharmaceuticals, medical equipment and solar panels.

A July 6, 2016 University of Florida news release, which originated the news item, provides more detail,

Nanoparticles can be “grown” in crystal formations with special use of light, in a process called plasmon-driven synthesis. However, scientists have had limited control unless they used silver, but silver limits the uses for medical technology. The team is the first to successfully use gold, which works well within the human body, with this process.

“How does light actually play a role in the synthesis? [This knowledge] was not well developed,” said David Wei, an associate professor of chemistry who led the research team. “Gold was the model system to demonstrate this.”

Gold is highly desired for nanotechnology because it is malleable, does not react with oxygen and conducts heat well. Those properties make gold an ideal material for nanoparticles, especially those that will be placed in the body.

When polyvinylpyrrolidone, or PVP, a substance commonly found in pharmaceutical tablets, is used in the plasmon-driven synthesis, it enables scientists to better control the growth of crystals. In Wei’s research, PVP surprised the team by showing its potential to relay light-generated “hot” electrons to a gold surface to grow the crystals.

The research describes the first plasmonic synthesis strategy that can make high-yield gold nanoprisms. Even more exciting, the team has demonstrated that visible-range and low-power light can be used in the synthesis. Combined with nanoparticles being used in solar photovoltaic devices, this method can even harness solar energy for chemical synthesis, to make nanomaterials or for general applications in chemistry.

Wei has spent the last decade working in nanotechnology. He is intrigued by its applications in photochemistry and biomedicine, especially in targeted drug delivery and photothermal therapeutics, which is crucial to cancer treatment. His team includes collaborators from Pacific Northwest National Laboratory, where he has worked as a visiting scholar, and Brookhaven National Laboratory. In addition, the project has provided an educational opportunity for chemistry students: one high school student (through UF’s Student Science Training Program), two University scholars who also [sic] funded by the Howard Hughes Medical Institute, five graduate students and two postdocs.

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

Polyvinylpyrrolidone-induced anisotropic growth of gold nanoprisms in plasmon-driven synthesis by Yueming Zhai, Joseph S. DuChene, Yi-Chung Wang, Jingjing Qiu, Aaron C. Johnston-Peck, Bo You, Wenxiao Guo, Benedetto DiCiaccio, Kun Qian, Evan W. Zhao, Frances Ooi, Dehong Hu, Dong Su, Eric A. Stach, Zihua Zhu, & Wei David Wei. Nature Materials (2016) doi:10.1038/nmat4683 Published online 04 July 2016

This paper is behind a paywall.

Pushing efficiency of perovskite-based solar cells to 31%

This atomic force microscopy image of the grainy surface of a perovskite solar cell reveals a new path to much greater efficiency. Individual grains are outlined in black, low-performing facets are red, and high-performing facets are green. A big jump in efficiency could possibly be obtained if the material can be grown so that more high-performing facets develop. (Credit: Berkeley Lab)

This atomic force microscopy image of the grainy surface of a perovskite solar cell reveals a new path to much greater efficiency. Individual grains are outlined in black, low-performing facets are red, and high-performing facets are green. A big jump in efficiency could possibly be obtained if the material can be grown so that more high-performing facets develop. (Credit: Berkeley Lab)

It’s always fascinating to observe a trend (or a craze) in science, an endeavour that outsiders (like me) tend to think of as impervious to such vagaries. Perovskite seems to be making its way past the trend/craze phase and moving into a more meaningful phase. From a July 4, 2016 news item on Nanowerk,

Scientists from the Department of Energy’s Lawrence Berkeley National Laboratory (Berkeley Lab) have discovered a possible secret to dramatically boosting the efficiency of perovskite solar cells hidden in the nanoscale peaks and valleys of the crystalline material.

Solar cells made from compounds that have the crystal structure of the mineral perovskite have captured scientists’ imaginations. They’re inexpensive and easy to fabricate, like organic solar cells. Even more intriguing, the efficiency at which perovskite solar cells convert photons to electricity has increased more rapidly than any other material to date, starting at three percent in 2009 — when researchers first began exploring the material’s photovoltaic capabilities — to 22 percent today. This is in the ballpark of the efficiency of silicon solar cells.

Now, as reported online July 4, 2016 in the journal Nature Energy (“Facet-dependent photovoltaic efficiency variations in single grains of hybrid halide perovskite”), a team of scientists from the Molecular Foundry and the Joint Center for Artificial Photosynthesis, both at Berkeley Lab, found a surprising characteristic of a perovskite solar cell that could be exploited for even higher efficiencies, possibly up to 31 percent.

A July 4, 2016 Berkeley Lab news release (also on EurekAlert), which originated the news item, details the research,

Using photoconductive atomic force microscopy, the scientists mapped two properties on the active layer of the solar cell that relate to its photovoltaic efficiency. The maps revealed a bumpy surface composed of grains about 200 nanometers in length, and each grain has multi-angled facets like the faces of a gemstone.

Unexpectedly, the scientists discovered a huge difference in energy conversion efficiency between facets on individual grains. They found poorly performing facets adjacent to highly efficient facets, with some facets approaching the material’s theoretical energy conversion limit of 31 percent.

The scientists say these top-performing facets could hold the secret to highly efficient solar cells, although more research is needed.

“If the material can be synthesized so that only very efficient facets develop, then we could see a big jump in the efficiency of perovskite solar cells, possibly approaching 31 percent,” says Sibel Leblebici, a postdoctoral researcher at the Molecular Foundry.

Leblebici works in the lab of Alexander Weber-Bargioni, who is a corresponding author of the paper that describes this research. Ian Sharp, also a corresponding author, is a Berkeley Lab scientist at the Joint Center for Artificial Photosynthesis. Other Berkeley Lab scientists who contributed include Linn Leppert, Francesca Toma, and Jeff Neaton, the director of the Molecular Foundry.

A team effort

The research started when Leblebici was searching for a new project. “I thought perovskites are the most exciting thing in solar right now, and I really wanted to see how they work at the nanoscale, which has not been widely studied,” she says.

She didn’t have to go far to find the material. For the past two years, scientists at the nearby Joint Center for Artificial Photosynthesis have been making thin films of perovskite-based compounds, and studying their ability to convert sunlight and CO2 into useful chemicals such as fuel. Switching gears, they created pervoskite solar cells composed of methylammonium lead iodide. They also analyzed the cells’ performance at the macroscale.

The scientists also made a second set of half cells that didn’t have an electrode layer. They packed eight of these cells on a thin film measuring one square centimeter. These films were analyzed at the Molecular Foundry, where researchers mapped the cells’ surface topography at a resolution of ten nanometers. They also mapped two properties that relate to the cells’ photovoltaic efficiency: photocurrent generation and open circuit voltage.

This was performed using a state-of-the-art atomic force microscopy technique, developed in collaboration with Park Systems, which utilizes a conductive tip to scan the material’s surface. The method also eliminates friction between the tip and the sample. This is important because the material is so rough and soft that friction can damage the tip and sample, and cause artifacts in the photocurrent.

Surprise discovery could lead to better solar cells

The resulting maps revealed an order of magnitude difference in photocurrent generation, and a 0.6-volt difference in open circuit voltage, between facets on the same grain. In addition, facets with high photocurrent generation had high open circuit voltage, and facets with low photocurrent generation had low open circuit voltage.

“This was a big surprise. It shows, for the first time, that perovskite solar cells exhibit facet-dependent photovoltaic efficiency,” says Weber-Bargioni.

Adds Toma, “These results open the door to exploring new ways to control the development of the material’s facets to dramatically increase efficiency.”

In practice, the facets behave like billions of tiny solar cells, all connected in parallel. As the scientists discovered, some cells operate extremely well and others very poorly. In this scenario, the current flows towards the bad cells, lowering the overall performance of the material. But if the material can be optimized so that only highly efficient facets interface with the electrode, the losses incurred by the poor facets would be eliminated.

“This means, at the macroscale, the material could possibly approach its theoretical energy conversion limit of 31 percent,” says Sharp.

A theoretical model that describes the experimental results predicts these facets should also impact the emission of light when used as an LED. …

The Molecular Foundry is a DOE Office of Science User Facility located at Berkeley Lab. The Joint Center for Artificial Photosynthesis is a DOE Energy Innovation Hub led by the California Institute of Technology in partnership with Berkeley Lab.

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

Facet-dependent photovoltaic efficiency variations in single grains of hybrid halide perovskite by Sibel Y. Leblebici, Linn Leppert, Yanbo Li, Sebastian E. Reyes-Lillo, Sebastian Wickenburg, Ed Wong, Jiye Lee, Mauro Melli, Dominik Ziegler, Daniel K. Angell, D. Frank Ogletree, Paul D. Ashby, Francesca M. Toma, Jeffrey B. Neaton, Ian D. Sharp, & Alexander Weber-Bargioni. Nature Energy 1, Article number: 16093 (2016  doi:10.1038/nenergy.2016.93 Published online: 04 July 2016

This paper is behind a paywall.

Dexter Johnson’s July 6, 2016 posting on his Nanoclast blog (on the IEEE [Institute of Electrical and Electronics Engineers] website} presents his take on the impact that this new finding may have,

The rise of the crystal perovskite as a potential replacement for silicon in photovoltaics has been impressive over the last decade, with its conversion efficiency improving from 3.8 to 22.1 percent over that time period. Nonetheless, there has been a vague sense that this rise is beginning to peter out of late, largely because when a solar cell made from perovskite gets larger than 1 square centimeter the best conversion efficiency had been around 15.6 percent. …

A 3D paper-based microbial fuel cell (MFC) from Iowa State University (US)

A July 1, 2016 news item on ScienceDaily proclaims the news about a paper-based microbial fuel cell (MFC),

A team of researchers from the Iowa State University in Ames, IA has demonstrated a proof-of-concept three-dimensional paper-based microbial fuel cell (MFC) that could take advantage of capillary action to guide the liquids through the MFC system and to eliminate the need for external power. …

A July 1, 2016 (?) World Scientific news release (also on EurekAlert), which originated the news item, describes the MFC in greater detail,

The paper-based MFC runs for five days and shows the production of current as a result of biofilm formation on anode. The system produces 1.3 µW of power and 52.25 µA of current yielding a power density of approximately 25 W/m3 for this experiment. These results show that the paper-based microbial fuel cells can create power in an environmentally friendly mode without the use of any outside power. “All power created in this device is useable because no electricity is needed to run the fluids through the device. This is crucial in the advancement of these devices and the expansion of their applications.” says Nastaran Hashemi, PhD, Assistant Professor of Mechanical Engineering and the senior author of the paper.

The biofilm formation on the carbon cloth during the test provides further evidence that the current measured was the result of the bio-chemical reaction taking place. This is important because the biofilm plays a vital role in current production of a microbial fuel cell. Increased biofilm size and thickness ultimately leads to increased current production. Individual bacterial cells metabolize electron-rich substances in a complex process involving many enzyme-catalyzed reactions. The electrons are then free to travel to the anode through one of many modes of electron transport. Electron transport is very complicated, and evidence suggests that it is unique to each type of bacteria. For Shewanella Oneidensis MR-1, the most predominantly known ways of shuttling electrons from the individual bacteria cells to the anode are through direct contact, excreted soluble redox molecules, and biological nanowires. Of these, it is widely believed that excreted soluble redox molecules serving as extracellular electron shuttles makes up for as much as 70% of electron transfer mechanisms from individual bacterial cells to the electrode. Moreover, it is shown that direct contact between individual S. Oneidensis MR-1 and the electrode has little impact on the current generation, supporting a mediated electron transfer mechanism. Biofilm helps with the adsorption of the redox molecules to the electrode, which makes it important to have in high power density microbial fuel cells. There are not many studies on power production from paper-based microbial fuel cells running for few days. Without enough time for biofilm to form, the reported current and power data would predominantly be associated with extracellular electron transfer, which represents does not fully represent electrical producing capabilities of microbial fuel cells. This device for the first time demonstrates the longer duration of use and ability to operate individually, a development that could help increase the number of situations where microbial fuel cells can be applied.

The Iowa State University team is currently exploring options to better control the voltage output and create constant current. Controlled environment tests will aid in the regulation of the systems output and yield more stable results. For optimal usability and decrease in cost, the team would also like to explore a device that would not need to use Nafion and Potassium Ferricyanide in its application. …

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

A paper-based microbial fuel cell operating under continuous flow condition by Niloofar Hashemi, Joshua M. Lackore, Farrokh Sharifi, Payton J. Goodrich, Megan L. Winchell, Nastaran Hashemi. Technology 04, 98 (2016). DOI: http://dx.doi.org/10.1142/S2339547816400124

I believe this paper is behind a paywall.

Photovoltaics as rose petals

Where solar cells (photovoltaics) are concerned, mimimicking plants is a longstanding pursuit. The latest  plant material to be mimicked is the rose petal’s surface. From a June 24, 2016 news item on ScienceDaily,

With a surface resembling that of plants, solar cells improve light-harvesting and thus generate more power. Scientists of KIT (Karlsruhe Institute of Technology) reproduced the epidermal cells of rose petals that have particularly good antireflection properties and integrated the transparent replicas into an organic solar cell. This resulted in a relative efficiency gain of twelve percent. …

Caption: Biomimetics: the epidermis of a rose petal is replicated in a transparent layer which is then integrated into the front of a solar cell. Credit Illustration: Guillaume Gomard, KIT

Caption: Biomimetics: the epidermis of a rose petal is replicated in a transparent layer which is then integrated into the front of a solar cell.
Credit Illustration: Guillaume Gomard, KIT

A June 24, 2016 KIT press release on EurekAlert, which originated the news item, expands on the theme,

Photovoltaics works in a similar way as the photosynthesis of plants. Light energy is absorbed and converted into a different form of energy. In this process, it is important to use a possibly large portion of the sun’s light spectrum and to trap the light from various incidence angles as the angle changes with the sun’s position. Plants have this capability as a result of a long evolution process – reason enough for photovoltaics researchers to look closely at nature when developing solar cells with a broad absorption spectrum and a high incidence angle tolerance.

Scientists at the KIT and the ZSW (Center for Solar Energy and Hydrogen Research Baden-Württemberg) now suggest in their article published in the Advanced Optical Materials journal to replicate the outermost tissue of the petals of higher plants, the so-called epidermis, in a transparent layer and integrate that layer into the front of solar cells in order to increase their efficiency.

First, the researchers at the Light Technology Institute (LTI), the Institute of Microstructure Technology (IMT), the Institute of Applied Physics (APH), and the Zoological Institute (ZOO) of KIT as well as their colleagues from the ZSW investigated the optical properties, and above all, the antireflection effect of the epidermal cells of different plant species. These properties are particularly pronounced in rose petals where they provide stronger color contrasts and thus increase the chance of pollination. As the scientists found out under the electron microscope, the epidermis of rose petals consists of a disorganized arrangement of densely packed microstructures, with additional ribs formed by randomly positioned nanostructures.

In order to exactly replicate the structure of these epidermal cells over a larger area, the scientists transferred it to a mold made of polydimethylsiloxane, a silicon-based polymer, pressed the resulting negative structure into optical glue which was finally left to cure under UV light. “This easy and cost-effective method creates microstructures of a depth and density that are hardly achievable with artificial techniques,” says Dr. Guillaume Gomard, Group Leader “Nanopothonics” at KIT’s LTI.

The scientists then integrated the transparent replica of the rose petal epidermis into an organic solar cell. This resulted in power conversion efficiency gains of twelve percent for vertically incident light. At very shallow incidence angles, the efficiency gain was even higher. The scientists attribute this gain primarily to the excellent omnidirectional antireflection properties of the replicated epidermis that is able to reduce surface reflection to a value below five percent, even for a light incidence angle of nearly 80 degrees. In addition, as examinations using a confocal laser microscope showed, every single replicated epidermal cell works as a microlense. The microlense effect extends the optical path within the solar cell, enhances the light-matter-interaction, and increases the probability that the photons will be absorbed.

“Our method is applicable to both other plant species and other PV technologies,” Guillaume Gomard explains. “Since the surfaces of plants have multifunctional properties, it might be possible in the future to apply multiple of these properties in a single step.” The results of this research lead to another basic question: What is the role of disorganization in complex photonic structures? Further studies are now examining this issue with the perspective that the next generation of solar cells might benefit from their results.

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

Flower Power: Exploiting Plants’ Epidermal Structures for Enhanced Light Harvesting in Thin-Film Solar Cells by Ruben Hünig, Adrian Mertens, Moritz Stephan, Alexander Schulz, Benjamin Richter, Michael Hetterich, Michael Powalla, Uli Lemmer, Alexander Colsmann, and Guillaume Gomard. Advanced Optical Materials  Version of Record online: 30 MAY 2016 DOI: 10.1002/adom.201600046

© 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

This paper is behind a paywall.

Dual purpose: loofah and battery?

Sadly, the proposed batteries are not dual purpose although they are based on loofah material. From a June 15, 2016 news item on phys.org,

Today’s mobile lifestyle depends on rechargeable lithium batteries. But to take these storage devices to the next level—to shore up the electric grid or for widespread use in vehicles, for example—they need a big boost in capacity. To get lithium batteries up to snuff for more ambitious applications, researchers report in the journal ACS Applied Materials & Interfaces a new solution that involves low-cost, renewable loofah sponges.

A June 15, 2016 American Chemical Society press release (also on EurekAlert), which originated the news item, expands on the theme,

The lithium-ion batteries that power most of our devices still have some room for improvement. But some experts predict that even when these batteries are fully optimized, they still will not be able to meet the power needs for larger-scale applications, such as taking a car 500 miles on one charge. Scientists looking to go beyond lithium-ion have turned to lithium-sulfur and other options. But a major challenge to commercializing these technologies remains: The cathodes crumble over time, leading to progressively lower capacity. Shanqing Zhang, Yanglong Hou, Li-Min Liu and colleagues wanted to find a way to stabilize these alternatives.

The researchers developed a “blocking” layer of highly conductive, porous carbon derived from a loofah sponge. The loofah-derived membrane helped prevent the cathode from dissolving in lithium-sulfur, lithium-selenium and lithium-iodine batteries — and all three types performed well consistently over 500 to 5,000 cycles. The loofah sponge carbon could be the advance needed to move these batteries forward in a low-cost, sustainable way, the researchers say.

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

Multifunctional Nitrogen-Doped Loofah Sponge Carbon Blocking Layer for High-Performance Rechargeable Lithium Batteries by Xingxing Gui, Chuan-Jia Tong, Sarish Rehman, Li-Min Liu, Yanglong Hou, and Shanqing Zhang. ACS Appl. Mater. Interfaces, Article ASAP DOI: 10.1021/acsami.6b02378 Publication Date (Web): June 02, 2016

Copyright © 2016 American Chemical Society

This paper is behind a paywall.

The researchers have made an image illustrating the work available,

Courtesy American Chemical Society

Courtesy American Chemical Society

Here’s one final bit from the press release,

The authors acknowledge funding from the Australian Research Council, the National Natural Science Foundation of China and the Ministry of Education of China.

Funding sources can be very interesting and this adds confirmation of China’s focus on the environment and sustainability.

Carrying a solar cell on a pencil or glass slide?

Caption: Ultra-thin solar cells are flexible enough to bend around small objects, such as the 1mm-thick edge of a glass slide, as shown here. Credit: Juho Kim, et al/ APL

Caption: Ultra-thin solar cells are flexible enough to bend around small objects, such as the 1mm-thick edge of a glass slide, as shown here. Credit: Juho Kim, et al/ APL

Yes, this is another wearable electronics story and this time, it’s from South Korea. A June 20, 2016 news item on ScienceDaily announces remarkably thin and flexible photovoltaics,

Scientists in South Korea have made ultra-thin photovoltaics flexible enough to wrap around the average pencil. The bendy solar cells could power wearable electronics like fitness trackers and smart glasses. …

A June 20, 2016 American Institute of Physics news release on EurekAlert, which originated the news item, expands on the theme,

Thin materials flex more easily than thick ones – think a piece of paper versus a cardboard shipping box. The reason for the difference: The stress in a material while it’s being bent increases farther out from the central plane. Because thick sheets have more material farther out they are harder to bend.

“Our photovoltaic is about 1 micrometer thick,” said Jongho Lee, an engineer at the Gwangju Institute of Science and Technology in South Korea. One micrometer is much thinner than an average human hair. Standard photovoltaics are usually hundreds of times thicker, and even most other thin photovoltaics are 2 to 4 times thicker.

The researchers made the ultra-thin solar cells from the semiconductor gallium arsenide. They stamped the cells directly onto a flexible substrate without using an adhesive that would add to the material’s thickness. The cells were then “cold welded” to the electrode on the substrate by applying pressure at 170 degrees Celcius and melting a top layer of material called photoresist that acted as a temporary adhesive. The photoresist was later peeled away, leaving the direct metal to metal bond.

The metal bottom layer also served as a reflector to direct stray photons back to the solar cells. The researchers tested the efficiency of the device at converting sunlight to electricity and found that it was comparable to similar thicker photovoltaics. They performed bending tests and found the cells could wrap around a radius as small as 1.4 millimeters.

The team also performed numerical analysis of the cells, finding that they experience one-fourth the amount of strain of similar cells that are 3.5 micrometers thick.

“The thinner cells are less fragile under bending, but perform similarly or even slightly better,” Lee said.

A few other groups have reported solar cells with thicknesses of around 1 micrometer, but have produced the cells in different ways, for example by removing the whole substract by etching.

By transfer printing instead of etching, the new method developed by Lee and his colleagues may be used to make very flexible photovoltaics with a smaller amount of materials.

The thin cells can be integrated onto glasses frames or fabric and might power the next wave of wearable electronics, Lee said.

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

Ultra-thin flexible GaAs photovoltaics in vertical forms printed on metal surfaces without interlayer adhesives by Juho Kim, Jeongwoo Hwang, Kwangsun Song, Namyun Kim, Jae Cheol Shin, and Jongho Lee. Appl. Phys. Lett. 108, 253101 (2016); http://dx.doi.org/10.1063/1.4954039

This paper is open access.

Turning gold into see-through rubber for an updated Rumpelstiltskin story

Rumpelstiltskin is a fairy tale whereby a young girl is trapped by her father’s lie that she can spin straw into gold. She is forced to spin gold by the King under pain of execution when an imp offers to help in exchange for various goods. As she succeeds each time, the King demands more until finally she has nothing left to trade for the imp’s help. Well, there is one last thing: her first-born child. She agrees to the bargain and she marries the King. On the birth of their first child, the imp reappears and under pressure of her pleas makes one last bargain. She must guess his name which she does, Rumplestiltskin. (The full story along with variants is here in this Wikipedia entry.)

With this latest research, we have a reverse Rumpelstiltskin story where gold is turned into something else according to a June 13, 2016 news item on Nanowerk (Note: A link has been removed),

Flexible solar panels that could be rolled up for easy transport and other devices would benefit from transparent metal electrodes that can conduct electricity, are stretchable, and resist damage following repeated stretching. Researchers found that topology and the adhesion between a metal nanomesh and the underlying substrate played key roles in creating such materials. The metal nanomesh can be stretched to three times its length while maintaining a transparency comparable to similar commercial materials used in solar cells and flat panel displays. Also, nanomeshes on pre-stretched slippery substrates led to electrodes that didn’t wear out, even after being stretched 50,000 times (Proceedings of the National Academy of Sciences, “Fatigue-free, superstretchable, transparent, and biocompatible metal electrodes”).

Tuning topology and adhesion of metal nanomeshes has led to super stretchable, transparent electrodes that don’t wear out. The scanning electron microscopy image shows the structure of a gold mesh created with a special lithographic technique that controlled the dimensions of the mesh structure. Optimizing this structure and its adhesion to the substrate was key to achieving super stretchability and long lifetimes in use—nanomeshes on pre-stretched slippery substrates did not show signs of wear even after repeated stretching, up to 50,000 cycles.

Tuning topology and adhesion of metal nanomeshes has led to super stretchable, transparent electrodes that don’t wear out. The scanning electron microscopy image shows the structure of a gold mesh created with a special lithographic technique that controlled the dimensions of the mesh structure. Optimizing this structure and its adhesion to the substrate was key to achieving super stretchability and long lifetimes in use—nanomeshes on pre-stretched slippery substrates did not show signs of wear even after repeated stretching, up to 50,000 cycles.

A June 9, 2016 US Dept. of Energy news release,which originated the news item, provides more detail,

Next-generation flexible electronics require highly stretchable and transparent electrodes. Fatigue, structural damage due to repeated use, is deadly in metals as it leads to poor conductivity and it commonly occurs in metals with repeated stretching—even with short elongations. However, few electronic conductors are transparent and stretchable, even fewer can be cyclically stretched to a large strain without causing fatigue. Now researchers led by the University of Houston found that optimizing topology of a metal nanomesh and its adhesion to an underlying substrate improved stretchability and eliminated fatigue, while maintaining transparency. A special lithographic technique called “grain boundary lithography” controlled the dimensions of the mesh structure. The metal nanomesh remained transparent after being stretched to three times its length. Gold nanomeshes on prestretched slippery substrates impressively showed no wear when stretched 50,000 times. The slippery surface advantageously allowed the structure of the nanomesh to reorient to relax the stress. Such electrically conductive, flexible, and transparent electrodes could lead to next-generation flexible electronics such as advanced solar cells.  The nanomesh electrodes are also promising for implantable electronics because the nanomeshes are biocompatible.

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

Fatigue-free, superstretchable, transparent, and biocompatible metal electrodes by Chuan Fei Guo, Qihan Liu, Guohui Wang, Yecheng Wang, Zhengzheng Shi, Zhigang Suo, Ching-Wu Chu, and Zhifeng Ren. Proceedings of the National Academy of Sciences, vol. 112 no. 40,  12332–12337, doi: 10.1073/pnas.1516873112

This paper appears to be open access.

Cleaning up nuclear waste gases with nanotechnology-enabled materials

Swiss and US scientists have developed a nanoporous crystal that could be used to clean up nuclear waste gases according to a June 13, 2016 news item on Nanowerk (Note: A link has been removed),

An international team of scientists at EPFL [École polytechnique fédérale de Lausanne in Switzerland] and the US have discovered a material that can clear out radioactive waste from nuclear plants more efficiently, cheaply, and safely than current methods.

Nuclear energy is one of the cheapest alternatives to carbon-based fossil fuels. But nuclear-fuel reprocessing plants generate waste gas that is currently too expensive and dangerous to deal with. Scanning hundreds of thousands of materials, scientists led by EPFL and their US colleagues have now discovered a material that can absorb nuclear waste gases much more efficiently, cheaply and safely. The work is published in Nature Communications (“Metal–organic framework with optimally selective xenon adsorption and separation”).

A June 14, 2016 EPFL press release (also on EurekAlert), which originated the news item, explains further,

Nuclear-fuel reprocessing plants generate volatile radionuclides such as xenon and krypton, which escape in the so-called “off-gas” of these facilities – the gases emitted as byproducts of the chemical process. Current ways of capturing and clearing out these gases involve distillation at very low temperatures, which is expensive in both terms of energy and capital costs, and poses a risk of explosion.

Scientists led by Berend Smit’s lab at EPFL (Sion) and colleagues in the US, have now identified a material that can be used as an efficient, cheaper, and safer alternative to separate xenon and krypton – and at room temperature. The material, abbreviated as SBMOF-1, is a nanoporous crystal and belongs a class of materials that are currently used to clear out CO2 emissions and other dangerous pollutants. These materials are also very versatile, and scientists can tweak them to self-assemble into ordered, pre-determined crystal structures. In this way, they can synthesize millions of tailor-made materials that can be optimized for gas storage separation, catalysis, chemical sensing and optics.

The scientists carried out high-throughput screening of large material databases of over 125,000 candidates. To do this, they used molecular simulations to find structures that can separate xenon and krypton, and under conditions that match those involved in reprocessing nuclear waste.

Because xenon has a much shorter half-life than krypton – a month versus a decade – the scientists had to find a material that would be selective for both but would capture them separately. As xenon is used in commercial lighting, propulsion, imaging, anesthesia and insulation, it can also be sold back into the chemical market to offset costs.

The scientists identified and confirmed that SBMOF-1 shows remarkable xenon capturing capacity and xenon/krypton selectivity under nuclear-plant conditions and at room temperature.

The US partners have also made an announcement with this June 13, 2016 Pacific Northwest National Laboratory (PNNL) news release (also on EurekAlert), Note: It is a little repetitive but there’s good additional information,

Researchers are investigating a new material that might help in nuclear fuel recycling and waste reduction by capturing certain gases released during reprocessing. Conventional technologies to remove these radioactive gases operate at extremely low, energy-intensive temperatures. By working at ambient temperature, the new material has the potential to save energy, make reprocessing cleaner and less expensive. The reclaimed materials can also be reused commercially.

Appearing in Nature Communications, the work is a collaboration between experimentalists and computer modelers exploring the characteristics of materials known as metal-organic frameworks.

“This is a great example of computer-inspired material discovery,” said materials scientist Praveen Thallapally of the Department of Energy’s Pacific Northwest National Laboratory. “Usually the experimental results are more realistic than computational ones. This time, the computer modeling showed us something the experiments weren’t telling us.”

Waste avoidance

Recycling nuclear fuel can reuse uranium and plutonium — the majority of the used fuel — that would otherwise be destined for waste. Researchers are exploring technologies that enable safe, efficient, and reliable recycling of nuclear fuel for use in the future.

A multi-institutional, international collaboration is studying materials to replace costly, inefficient recycling steps. One important step is collecting radioactive gases xenon and krypton, which arise during reprocessing. To capture xenon and krypton, conventional technologies use cryogenic methods in which entire gas streams are brought to a temperature far below where water freezes — such methods are energy intensive and expensive.

Thallapally, working with Maciej Haranczyk and Berend Smit of Lawrence Berkeley National Laboratory [LBNL] and others, has been studying materials called metal-organic frameworks, also known as MOFs, that could potentially trap xenon and krypton without having to use cryogenics.

These materials have tiny pores inside, so small that often only a single molecule can fit inside each pore. When one gas species has a higher affinity for the pore walls than other gas species, metal-organic frameworks can be used to separate gaseous mixtures by selectively adsorbing.

To find the best MOF for xenon and krypton separation, computational chemists led by Haranczyk and Smit screened 125,000 possible MOFs for their ability to trap the gases. Although these gases can come in radioactive varieties, they are part of a group of chemically inert elements called “noble gases.” The team used computing resources at NERSC, the National Energy Research Scientific Computing Center, a DOE Office of Science User Facility at LBNL.

“Identifying the optimal material for a given process, out of thousands of possible structures, is a challenge due to the sheer number of materials. Given that the characterization of each material can take up to a few hours of simulations, the entire screening process may fill a supercomputer for weeks,” said Haranczyk. “Instead, we developed an approach to assess the performance of materials based on their easily computable characteristics. In this case, seven different characteristics were necessary for predicting how the materials behaved, and our team’s grad student Cory Simon’s application of machine learning techniques greatly sped up the material discovery process by eliminating those that didn’t meet the criteria.”

The team’s models identified the MOF that trapped xenon most selectively and had a pore size close to the size of a xenon atom — SBMOF-1, which they then tested in the lab at PNNL.

After optimizing the preparation of SBMOF-1, Thallapally and his team at PNNL tested the material by running a mixture of gases through it — including a non-radioactive form of xenon and krypton — and measuring what came out the other end. Oxygen, helium, nitrogen, krypton, and carbon dioxide all beat xenon out. This indicated that xenon becomes trapped within SBMOF-1’s pores until the gas saturates the material.

Other tests also showed that in the absence of xenon, SBMOF-1 captures krypton. During actual separations, then, operators would pass the gas streams through SBMOF-1 twice to capture both gases.

The team also tested SBMOF-1’s ability to hang onto xenon in conditions of high humidity. Humidity interferes with cryogenics, and gases must be dehydrated before putting them through the ultra-cold method, another time-consuming expense. SBMOF-1, however, performed quite admirably, retaining more than 85 percent of the amount of xenon in high humidity as it did in dry conditions.

The final step in collecting xenon or krypton gas would be to put the MOF material under a vacuum, which sucks the gas out of the molecular cages for safe storage. A last laboratory test examined how stable the material was by repeatedly filling it up with xenon gas and then vacuuming out the xenon. After 10 cycles of this, SBMOF-1 collected just as much xenon as the first cycle, indicating a high degree of stability for long-term use.

Thallapally attributes this stability to the manner in which SBMOF-1 interacts with xenon. Rather than chemical reactions between the molecular cages and the gases, the relationship is purely physical. The material can last a lot longer without constantly going through chemical reactions, he said.

A model finding

Although the researchers showed that SBMOF-1 is a good candidate for nuclear fuel reprocessing, getting these results wasn’t smooth sailing. In the lab, the researchers had followed a previously worked out protocol from Stony Brook University to prepare SBMOF-1. Part of that protocol requires them to “activate” SBMOF-1 by heating it up to 300 degrees Celsius, three times the temperature of boiling water.

Activation cleans out material left in the pores from MOF synthesis. Laboratory tests of the activated SBMOF-1, however, showed the material didn’t behave as well as it should, based on the computer modeling results.

The researchers at PNNL repeated the lab experiments. This time, however, they activated SBMOF-1 at a lower temperature, 100 degrees Celsius, or the actual temperature of boiling water. Subjecting the material to the same lab tests, the researchers found SBMOF-1 behaving as expected, and better than at the higher activation temperature.

But why? To figure out where the discrepancy came from, the researchers modeled what happened to SBMOF-1 at 300 degrees Celsius. Unexpectedly, the pores squeezed in on themselves.

“When we heated the crystal that high, atoms within the pore tilted and partially blocked the pores,” said Thallapally. “The xenon doesn’t fit.”

Armed with these new computational and experimental insights, the researchers can explore SBMOF-1 and other MOFs further for nuclear fuel recycling. These MOFs might also be able to capture other noble gases such as radon, a gas known to pool in some basements.

Researchers hailed from several other institutions as well as those listed earlier, including University of California, Berkeley, Ecole Polytechnique Fédérale de Lausanne (EPFL) in Switzerland, Brookhaven National Laboratory, and IMDEA Materials Institute in Spain. This work was supported by the [US] Department of Energy Offices of Nuclear Energy and Science.

Here’s an image the researchers have provided to illustrate their work,

Caption: The crystal structure of SBMOF-1 (green = Ca, yellow = S, red = O, gray = C, white = H). The light blue surface is a visualization of the one-dimensional channel that SBMOF-1 creates for the gas molecules to move through. The darker blue surface illustrates where a Xe atom sits in the pores of SBMOF-1 when it adsorbs. Credit: Berend Smit/EPFL/University of California Berkley

Caption: The crystal structure of SBMOF-1 (green = Ca, yellow = S, red = O, gray = C, white = H). The light blue surface is a visualization of the one-dimensional channel that SBMOF-1 creates for the gas molecules to move through. The darker blue surface illustrates where a Xe atom sits in the pores of SBMOF-1 when it adsorbs. Credit: Berend Smit/EPFL/University of California Berkley

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

Metal–organic framework with optimally selective xenon adsorption and separation by Debasis Banerjee, Cory M. Simon, Anna M. Plonka, Radha K. Motkuri, Jian Liu, Xianyin Chen, Berend Smit, John B. Parise, Maciej Haranczyk, & Praveen K. Thallapally. Nature Communications 7, Article number: ncomms11831  doi:10.1038/ncomms11831 Published 13 June 2016

This paper is open access.

Final comment, this is the second time in the last month I’ve stumbled across more positive approaches to nuclear energy. The first time was a talk (Why Nuclear Power is Necessary) held in Vancouver, Canada in May 2016 (details here). I’m not trying to suggest anything unduly sinister but it is interesting since most of my adult life nuclear power has been viewed with fear and suspicion.

A new, stable open-shell carbon molecule from Oregon

This discovery could one day make organic solar cells more efficient than silicon ones. Researchers at the University of Oregon announced their discovery in a June 9, 2016 news item on ScienceDaily,

University of Oregon chemists have synthesized a stable and long-lasting carbon-based molecule that, they say, potentially could be applicable in solar cells and electronic devices.

The molecule changes its bonding patterns to a magnetic biradical state when heated; it then returns to a fully bonded non-magnetic closed state at room temperature. That transition, they report, can be done repeatedly without decomposition. It remains stable in the presence of both heat and oxygen.

A June 9, 2016 University of Oregon news release on EurekAlert, which originated the news item, provides more detail,

 

Biradical refers to organic compounds, known as open-shell molecules, that have two free-flowing, non-bonding electrons. Producing them using techniques to control their electron spin, and thus provide semiconducting properties, in a heated state has been hampered by instability since the first synthetic biradical hydrocarbon was made in 1907.

“Potentially our approach could help to make organic solar cells more efficient than silicon solar cells, but that’s probably far in the future,” said UO doctoral student Gabriel E. Rudebusch, the paper’s lead author. “Our synthesis is rapid and efficient. We easily can make a gram of this compound, which is very stable when exposed to oxygen and heat. This stability has been almost unheard of in the literature about biradical compounds.”

The four-step synthesis of the compound — diindenoanthracene, or DIAn — and how it held up when tested in superconducting materials were detailed in a proof-of-principle paper published online May 23 by the journal Nature Chemistry. The UO team collaborated with experts in Japan, Spain and Sweden.

The molecular framework for the new molecule involves the hydrocarbon anthracene, which has three linearly fused hexagonal benzene rings, in combination with two five-membered pentagonal rings.

“The big difference between our new molecule and a lot of other biradical molecules that have been produced is those five-membered rings,” said co-author Michael M. Haley, who holds the UO’s Richard M. and Patricia H. Noyes Professorship in Chemistry. “They have the inherent ability to accept electrons or give up electrons. This means DIAn can move both negative and positive charges, which is an essential property for useful devices such as transistors and solar cells. Also, we can heat up our molecule to 150 degrees Celsius, bring it back to room temperature and heat it up again, repeatedly, and we see no decomposition in its reaction to oxygen. The unique features of DIAn are essential if these molecules are to have a use in the real world.”

Haley’s lab is now seeking to develop derivatives of the new molecule to help move the technology forward into potential applications.

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

Diindeno-fusion of an anthracene as a design strategy for stable organic biradicals by Gabriel E. Rudebusch, José L. Zafra, Kjell Jorner, Kotaro Fukuda, Jonathan L. Marshall, Iratxe Arrechea-Marcos, Guzmán L. Espejo, Rocío Ponce Ortiz, Carlos J. Gómez-García, Lev N. Zakharov, Masayoshi Nakano, Henrik Ottosson, Juan Casado & Michael M. Haley. Nature Chemistry (2016)  doi:10.1038/nchem.2518 Published online 23 May 2016

This paper is behind a paywall.

There is another June 9, 2016 University of Oregon news release by Jim Barlow about this discovery. It covers much of the same material but focuses more closely on Rudebusch’s perspective.