Chemists turn gold to purple -- on purpose

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Professor Richard Watt and his chemistry students suspected that a common protein could potentially react with sunlight and harvest its energy– similar to what chlorophyll does during photosynthesis.

The story of how they proved it sounds as colorful as the legend of the leprechaun who hid his pot ofgoldat the end of the rainbow.

They started with citric acid from oranges and mixed it with the protein. Next they dissolved gold powder into the solution. Then they put vials of the yellow-colored mixture in direct sunlight and crossed their fingers in the hope that it would turn purple.

Here's the reason why: If it turned purple, that would signal that the gold atoms had received electrons and used the donated energy to bunch together as small, purple-colorednanoparticles. And that would mean that the protein used the sunlight to excite the citric acid and trigger a transfer of energy.

While direct sunlight did the trick in about 20 minutes, a high-powered tungsten mercury lamp worked much faster.

"We set the system up, turned on the light, and the solution turned purple,"Watt said."We knew that we'd proved the concept."

The beauty of this experiment lies not in its colors– unless, of course, you're thinking of it as a potential"green"energy source that keeps the environment clean.

The BYU researchers published their experiments in theJournal of Nanoparticle Research. The final step of this project will involve connecting theproteinto an electrode to channel the energy into a battery or fuel cell. The BYU chemists will partner with Jae-Woo Kim of the National Institute of Aerospace for this next stage of the work.

Professor Watt's pedigree includes a post-doc at Princeton, a father who developed a fuel cell that runs on sugar and weed-killer and a more distant ancestor credited with inventing the first practical steam engine. That ancestor is also the Scottish engineer for whom the unit of power"watt"is named.

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New approach to solar cells

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An interdisciplinary team of UC Davis and UC Santa Cruz researchers is taking a novel approach to solar power, one that promises to lead to a technological breakthrough. By using nanoparticles of germanium, silicon and other materials, the researchers hope to produce solar cells far more efficient than the current state of the art.

The project was recently awarded $1.5 million over three years from the National Science Foundation.

Conventional solar cells all operate on the same principle of"one photon in, one electron out,"said Gergely Zimanyi, professor of physics at UC Davis and principal investigator on the NSF grant. In other words, one particle of light, or photon, hits the solar cell and generates one electron to produce an electrical current.

The efficiency— energy out compared to energy in— of a solar cell operating according to this principle is capped by a theoretical maximum of 31 percent. But by constructing solar cells from extremely small nanoparticles, the UC researchers aim to generate severalelectronsfor each photon, raising the maximum efficiency to between 42 and 65 percent.

The one-photon-in/multiple-electrons-out paradigm has been demonstrated at the Los Alamos National Laboratory, Zimanyi said— but the Los Alamos group did not build a functioning solar cell based on this paradigm. The UC Davis/UC Santa Cruz team includes scientists with experience makingsolar cellsfrom nanoparticles, giving hope that the group will be able to construct a fully functioning and well-optimized solar cell fromgermaniumandsiliconnanoparticles, he said.

The team members are: Zimanyi; UC Davis chemistry professors Susan Kauzlarich and Delmar Larsen; Professor Giulia Galli, who holds a joint appointment in physics and chemistry; Professor Zhaojun Bai, Department of Mathematics and Computer Science; Debashis Paul, professor in the Department of Statistics; and Susan Carter, professor of physics at UC Santa Cruz.

The interdisciplinary nature of the team was crucial to getting the proposal funded, Zimanyi said."NSF asked for a collaborative effort between materials sciences, chemistry and mathematical sciences,"he said.

Zimanyi, Galli and Bai will conduct theoretical and computer-modeling studies, with Paul providing statistical expertise; Kauzlarich's lab will synthesize the newnanoparticles, Larsen's group will characterize them and Carter's lab at UCSC will develop a working device. A prototype cell has been already constructed prior to getting the grant and exhibited an efficiency of about 8 percent, which Zimanyi described as a very encouraging result given the limited resources going into its construction.

The team will collaborate with the California Solar Energy Collaborative, which is based at UC Davis and led by Pieter Stroeve, professor of chemical engineering and materials science. The team also plans an outreach effort, primarily via its public webpage:http://www.solarwi… cdavis.edu/.

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A mix of tiny gold and viral particles -- and the DNA ties that bind them

Scientists have created a diamond-like lattice composed of gold nanoparticles and viral particles, woven together and held in place by strands of DNA. The structure– a distinctive mix of hard, metallic nanoparticles and organic viral pieces known as capsids, linked by the very stuff of life, DNA– marks a remarkable step in scientists' ability to combine an assortment of materials to create infinitesimal devices.

The research, done by scientists at the University of Rochester Medical Center, Scripps Research Institute, and Massachusetts Institute of Technology, was published recently inNature Materials.

While people commonly think ofDNAas a blueprint for life, the team used DNA instead as a tool to guide the precise positioning of tiny particles just one-millionth of a centimeter across, using DNA to chaperone the particles.

Central to the work is the unique attraction of each of DNA's four chemical bases to just one other base. The scientists created specific pieces of DNA and then attached them to gold nanoparticles and viral particles, choosing the sequences and positioning them exactly to force the particles to arrange themselves into a crystal lattice.

When scientists mixed the particles, out of the brew emerged a sodium thallium crystal lattice. The device"self assembled"or literally built itself.

The research adds some welcome flexibility to the toolkit that scientists have available to create nano-sized devices.

"Organic materials interact in ways very different from metal nanoparticles. The fact that we were able to make such different materials work together and be compatible in a single structure demonstrates some new opportunities for building nano-sized devices,"said Sung Yong Park, Ph.D., a research assistant professor of Biostatistics and Computational Biology at Rochester.

Park and M.G Finn, Ph.D., of Scripps Research Institute are corresponding authors of the paper.

Such a crystal lattice is potentially a central ingredient to a device known as a photonic crystal, which can manipulate light very precisely, blocking certain colors or wavelengths of light while letting other colors pass. While 3-D photonic crystals exist that can bend light at longer wavelengths, such as the infrared, this lattice is capable of manipulating visible light. Scientists foresee many applications for such crystals, such as optical computing and telecommunications, but manufacturing and durability remain serious challenges.

It was three years ago that Park, as part of a larger team of colleagues at Northwestern University, first produced a crystal lattice with a similar method, using DNA to link gold nanospheres. The new work is the first to combine particles with such different properties– hard goldnanoparticlesand more flexible organic particles.

Within the new structure, there are actually two distinct forces at work, Park said. Thegoldparticles and theviral particlesrepel each other, but their deterrence is countered by the attraction between the strategically placed complementary strands of DNA. Both phenomena play a role in creating the rigidcrystal lattice. It's a little bit like how countering forces keep our curtains up: A spring in a curtain rod pushes the rod to lengthen, while brackets on the window frame counter that force, creating a taut, rigid device.

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A paperweight for platinum: Bracing catalyst in material makes fuel cell component work better, last longer

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A new combination of nanoparticles and graphene results in a more durable catalytic material for fuel cells, according to work published today online at the Journal of the American Chemical Society. The catalytic material is not only hardier but more chemically active as well. The researchers are confident the results will help improve fuel cell design.

"Fuel cells are an important area of energy technology, but cost and durability are big challenges,"said chemist Jun Liu."The unique structure of this material provides much needed stability, goodelectrical conductivityand other desired properties."

Liu and his colleagues at the Department of Energy's Pacific Northwest National Laboratory, Princeton University in Princeton, N.J., and Washington State University in Pullman, Wash., combined graphene, a one-atom-thick honeycomb of carbon with handy electrical and structural properties, withmetal oxidenanoparticles to stabilize afuel cellcatalystand make it better available to do its job.

"This material has great potential to make fuel cells cheaper and last longer,"said catalytic chemist Yong Wang, who has a joint appointment with PNNL and WSU."The work may also provide lessons for improving the performance of other carbon-based catalysts for a broad range of industrial applications."

Muscle Metal Oxide

Fuel cells work by chemically breaking down oxygen and hydrogen gases to create an electrical current, producing water and heat in the process. The centerpiece of the fuel cell is the chemical catalyst -- usually a metal such asplatinum-- sitting on a support that is often made of carbon. A good supporting material spreads the platinum evenly over its surface to maximize the surface area with which it can attackgas molecules. It is also electrically conductive.

Fuel cell developers most commonly useblack carbon-- think pencil lead -- but platinum atoms tend to clump on such carbon. In addition, water can degrade the carbon away. Another support option is metal oxides -- think rust -- but what metal oxides make up for in stability and catalyst dispersion, they lose in conductivity and ease of synthesis. Other researchers have begun to explore metal oxides in conjunction with carbon materials to get the best of both worlds.

As a carbon support, Liu and his colleagues thought graphene intriguing. The honeycomb lattice of graphene is porous, electrically conductive and affords a lot of room for platinum atoms to work. First, the team crystallized nanoparticles of the metal oxide known as indium tin oxide -- or ITO -- directly onto specially treated graphene. Then they added platinum nanoparticles to the graphene-ITO and tested the materials.

Platinumweight

The team viewed the materials under high-resolution microscopes at EMSL, DOE's Environmental Molecular Sciences Laboratory on the PNNL campus. The images showed that without ITO, platinum atoms clumped up on the graphene surface. But with ITO, the platinum spread out nicely. Those images also showed catalytic platinum wedged between the nanoparticles and the graphene surface, with the nanoparticles partially sitting on the platinum like a paperweight.

To see how stable this arrangement was, the team performed theoretical calculations of molecular interactions between the graphene, platinum and ITO. This number-crunching on EMSL's Chinook supercomputer showed that the threesome was more stable than the metal oxide alone on graphene or the catalyst alone on graphene.

But stability makes no difference if the catalyst doesn't work. In tests for how well the materials break down oxygen as they would in a fuel cell, the triple-threat packed about 40% more of a wallop than the catalyst alone on graphene or the catalyst alone on other carbon-based supports such as activated carbon.

Last, the team tested how well the new material stands up to repeated usage by artificially aging it. After aging, the tripartite material proved to be three times as durable as the lone catalyst ongrapheneand twice as durable as on commonly used activated carbon. Corrosion tests revealed that the triple threat was more resistant than the other materials tested as well.

The team is now incorporating the platinum-ITO-graphene material into experimental fuel cells to determine how well it works under real world conditions and how long it lasts.

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A new type of composite material with peapod structures can help improve performance of lithium-ion batteries

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Lithium-ion batteries are used to power a wide range of electronic devices, including computers, cameras, digital audio players and calculators. Tremendous effort has been devoted to the development of lithium-ion batteries, especially in improving the efficiency and integrity of the battery electrodes. This is because during the discharging and charging processes, lithium ions are repeatedly incorporated into and extracted from the electrodes by alloy formation or chemical conversion. These recurring events are known to cause the progressive degradation of the electrodes, irreversibly damaging battery performance.

Yu Wang at the A*STAR Institute of Chemical and Engineering Sciences and co-workers have now demonstrated an elegant strategy to reduce the degradation problem and increase the capacity retention of lithium-ion batteries over many charge–discharge cycles. The strategy involves the use of acomposite materialwith a peapod structure comprising cobalt oxide (Co₃O₄) nanoparticles embedded in carbon fibers (see image).

Cobalt oxide is a promising material for anodes in lithium-ion batteries because its capacity for holding ions is higher than that of conventional electrode materials, such as tin. In addition, Co₃O₄can be easily converted to LiCoO₂, which is the material currently used in commercial cathodes. The researchers made the peapod structures by heating cobalt carbonate hydroxide nanobelts coated with layers of polymerized glucose in an inert atmosphere at 700ºC and then in air at 250ºC. Electrodes built using the peapod composite had enhancedlithiumstorage and capacity retention—delivering 91% of the total possible capacity after 50 charge–discharge cycles.

“The Co₃O₄nanoparticles act as active materials to store lithium ions and the hollow carbon fibers protect and prevent the Co3O4 nanoparticles from aggregating and collapsing,” says Wang. Thecarbon fibersalso play the role of conducting electrons from the nanoparticles.

According to Wang, aside from the promising application in lithium-ion batteries, the fabrication of the peapod composite is an achievement in itself, as it is the first time that such isolated magnetic nanoparticles embedded in hollow fibers have been produced. Scanning electron microscopy revealed that the peapod composite exhibits a uniform morphology, with pod lengths of up to several micrometers and pod diameters of as small as 50 nanometers. The researchers believe that their method could be extended to generate encapsulated nanoparticles using a wide range of materials with applications beyond lithium-ion batteries, for example, in gene engineering, catalysis, gas sensing and the manufacture of capacitors and magnets.

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A dash of disorder yields a very efficient photocatalyst

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(PhysOrg.com) -- A little disorder goes a long way, especially when it comes to harnessing the sun’s energy. Scientists from the U.S. Department of Energy’s Lawrence Berkeley National Laboratory (Berkeley Lab) jumbled the atomic structure of the surface layer of titanium dioxide nanocrystals, creating a catalyst that is both long lasting and more efficient than all other materials in using the sun’s energy to extract hydrogen from water.

Their photocatalyst, which accelerates light-driven chemical reactions, is the first to combine durability and record-breaking efficiency, making it a contender for use in several clean-energy technologies.

It could offer a pollution-free way to producehydrogenfor use as an energy carrier in fuel cells. Fuel cells have been eyed as an alternative to combustion engines in vehicles. Molecular hydrogen, however, exists naturally on Earth only in very low concentrations. It must be extracted from feedstocks such as natural gas or water, an energy-intensive process that is one of the barriers to the widespread implementation of the technology.

“We are trying to find better ways to generate hydrogen from water using sunshine,” says Samuel Mao, a scientist in Berkeley Lab’s Environmental Energy Technologies Division who led the research.“In this work, we introduced disorder in titanium dioxide nanocrystals, which greatly improves its light absorption ability and efficiency in producing hydrogen from water.”

Mao is the corresponding author of a paper on this research that was published online Jan. 20, 2011 inScience Expresswith the title“Increasing Solar Absorption for Photocatalysis with Black, Hydrogenated Titanium Dioxide Nanocrystals.” Co-authoring the paper with Mao are fellow Berkeley Lab researchers Xiaobo Chen, Lei Liu, and Peter Yu.

Mao and his research group started with nanocrystals of titanium dioxide, which is a semiconductor material that is used as a photocatalyst to accelerate chemical reactions, such as harnessing energy from the sun to supply electrons that split water into oxygen and hydrogen. Although durable, titanium dioxide isn’t a very efficient photocatlayst. Scientists have worked to increase its efficiency by adding impurities and making other modifications.

The Berkeley Lab scientists tried a new approach. In addition to adding impurities, they engineered disorder into the ordinarily perfect atom-by-atom lattice structure of the surface layer of titanium dioxide nanocrystals. This disorder was introduced via hydrogenation.

The result is the first disorder-engineered nanocrystal. One transformation was obvious: the usually white titanium dioxide nanocrystals turned black, a sign that engineered disorder yielded infrared absorption.

The scientists also surmised disorder boosted the photocatalyst’s performance. To find out if their hunch was correct, they immersed disorder-engineered nanocrystals in water and exposed them to simulated sunlight. They found that 24 percent of the sunlight absorbed by the photocatalyst was converted into hydrogen, a production rate that is about 100 times greater than the yields of most semiconductor photocatalysts.

In addition, their photocatalyst did not show any signs of degradation during a 22-day testing period, meaning it is potentially durable enough for real-world use.

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Berkeley Lab scientist Samuel Mao leads a research team that is searching for sustainable ways to generate hydrogen for use in clean-energy technologies. In a first-of-its-kind development, they jumbled the surface layer of titanium dioxide nanocrystals, a feat that turned the material from white to black. It also created a photocatalyst whose efficiency outpaces others in using the sun’s energy to extract hydrogen from water. (Photo by Roy Kaltschmidt, Berkeley Lab Public Affairs)

Its landmark efficiency stems largely from the photocatalyst’s ability to absorb infrared light, making it the first titanium dioxide photocatalyst to absorb light in this wavelength. It also absorbs visible and ultraviolet light. In contrast, most titanium dioxide photocatalysts only absorbs ultraviolet light, and those containing defects may absorb visible light. Ultraviolet light accounts for less than ten percent of solar energy.

“The more energy from the sun that can be absorbed by aphotocatalyst, the more electrons can be supplied to a chemical reaction, which makes blacktitanium dioxidea very attractive material,” says Mao, who is also an adjunct engineering professor in the University of California at Berkeley.

The team’s intriguing experimental findings were further elucidated by theoretical physicists Peter Yu and Lei Liu, who explored how jumbling the latticework of atoms on the nanocrystal’s surface via hydrogenation changes its electronic properties. Their calculations revealed that disorder, in the form of lattice defects and hydrogen, makes it possible for incoming photons to excite electrons, which then jump across a gap where no electron states can exist. Once across this gap, the electrons are free to energize the chemical reaction that splits water into hydrogen and oxygen.

“By introducing a specific kind of disorder, mid-gap electronic states are created accompanied by a reduced band gap,” says Yu, who is also a professor in the University of California at Berkeley’s Physics Department.“This makes it possible for the infrared part of the solar spectrum to be absorbed and contribute to the photocatalysis.”

This research was supported by the Department of Energy’s Office of Energy Efficiency and Renewable Energy. Transmission electron microscopy imaging used to study the nanocrystals at the atomic scale was performed at the National Center for Electron Microscopy, a national user facility located at Berkeley Lab.

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Touchscreens made of carbon

Touchscreens are in -- although the technology still has its price. The little screens contain rare and expensive elements. This is the reason why researchers at Fraunhofer are coming up with an alternative display made of low-priced renewable raw materials available all over the world. The researchers are presenting touchscreens that contain carbon nanotubes at the nano tech 2011 fair in Tokyo from Feb. 16-18.

Just touching it slightly with the tips of your fingers is enough. You can effortlessly write, navigate, open menu windows or rotate images on touchscreens. Within fractions of a second your touch is translated into control commands that a computer understands. At first glance, this technology borders on the miraculous, but in real life this mystery just is a wafer-thin electrode under theglass surfaceof the display made of indium-tin-oxide, ITO. This material is nothing short of ideal for use in touchscreens because it is excellent at conducting slight currents and lets the colors of the display pass through unhindered. But, there is a little problem: there are very few deposits of indium anywhere in the world. In the long term, the manufacturers of electronic gadgets are afraid that they will be dependent upon the prices set by suppliers. This is the reason why indium is one of what people call"strategic metals."

Therefore, private industry is very interested in alternatives to ITO that are similarly efficient. The researchers at Fraunhofer have succeeded at coming up with a new material forelectrodesthat is on the same level as ITO and on top of it is much cheaper. Its main components arecarbonnanotubes and low-cost polymers. This new electrode foil is composed of two layers. One is the carrier, a thin foil made of inexpensive polyethylenterephthalate PET used for making plastic bottles. Then a mixture of carbon-nanotubes and electrically conducting polymers is added that is applied to the PET as a solution and forms a thin film when it dries.

In comparison to ITO, these combinations of plastics have not been particularly durable because humidity, pressure or UV light put a strain on the polymers. The layers became brittle and broke down. Only carbon nanotubes have made them stable. The carbon nanotubes harden on the PET to create a network where the electrically conducting polymers can be firmly anchored. That means that this layer is durable in the long run. Ivica Kolaric, project manager from Fraunhofer Institute for Manufacturing Engineering and Automation IPA, concedes that"the electrical resistance of our layer is somewhat greater than that of the ITO, but it's easily enough for an application in electrical systems."Its merits are unbeatable: carbon is not only low-cost and available all over the world. It is also a renewable resource that you can get from organic matter such as wood. Kolaric and his colleagues will be presenting their carbon touchdisplay at the 2011 nano tech fair. Since 2003 Fraunhofer researchers show their developments at the annual trade show.

There are a whole series of implementations for the new technology. This foil is flexible and can be used in a variety of ways. Kolaric sums up by saying"we could even make photovoltaic foils out of it to line corrugated roofs or other uneven structures."The researcher has already set up pilot production where the foil can be enhanced for a wide range of applications.

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