Nanonets give rust a boost as agent in water splitting's hydrogen harvest

Coating a lattice of tiny wires called Nanonets with iron oxide (rust) creates an economical and efficient platform for the process of water splitting -- an emerging clean fuel method that harvests hydrogen from water, Boston College researchers report in the online edition of the Journal of the American Chemical Society.

Assistant Professor of Chemistry Dunwei Wang and his clean energy lab pioneered the development of Nanonets in 2008 and have since shown them to be a viable new platform for a number of energy applications by virtue of the increased surface area and improved conductivity of the nano-scale netting made from titanium disilicide, a readily available semiconductor.

Wang and his team report that coating the Nanonets with hematite, the plentiful mineral form of iron oxide, showed the mineral could absorb light efficiently and without the added expense of enhancing the material with an oxygen evolving catalyst.

The results flow directly from the introduction of the Nanonet platform, Wang said. While constructed of wires 1/400th the size of a human hair, Nanonets are highly conductive and offer significant surface area. They serve dual roles as a structural support and an efficient charge collector, allowing for maximum photon-to-charge conversion, Wang said.

"Recent research has shown that the use of a catalyst can boost the performance of hematite," said Wang. "What we have shown is the potential performance of hematite at its fundamental level, without a catalyst. By using this unique Nanonet structure, we have shed new light on the fundamental performance capabilities of hematite in water splitting."

On its own, hematite faces natural limits in its ability to transport a charge. A photon can be absorbed, but has no place to go. By giving it structure and added conductivity, the charge transport abilities of hematite increase, said Wang. Water splitting, a chemical reaction that separates water into oxygen and hydrogen gas, can be initiated by passing an electric current through water. But that process is expensive, so gains in efficiency and conductivity are required to make large-scale water splitting an economically viable source for clean energy, Wang said.

"The result highlights the importance of charge transport in semiconductor-based water splitting, particularly for materials whose performance is limited by poor charge diffusion," the researchers report in the journal. "Our design introduces material components to provide a dedicated charge transport pathway, alleviates the reliance on the materials' intrinsic properties, and therefore has the potential to greatly broaden where and how various existing materials can be used in energy-related applications."

Story Source:

The above story is reprinted (with editorial adaptations by ScienceDaily staff) from materials provided by Boston College, via EurekAlert!, a service of AAAS.

Journal Reference:

Yongjing Lin, Sa Zhou, Stafford W. Sheehan, Dunwei Wang. Nanonet-Based Hematite Heteronanostructures for Efficient Solar Water Splitting. Journal of the American Chemical Society, 2011; 110209093040054 DOI: 10.1021/ja110741z

Note: If no author is given, the source is cited instead.

Disclaimer: Views expressed in this article do not necessarily reflect those of ScienceDaily or its staff.

Paperweight for platinum: Bracing catalyst in material makes fuel cell component work better and last longer

A new combination of nanoparticles and graphene results in a more durable catalytic material for fuel cells, according to work published 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, good electrical conductivity and 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, with metal oxide nanoparticles to stabilize a fuel cell catalyst and 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 as platinum -- 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 attack gas molecules. It is also electrically conductive.

Fuel cell developers most commonly use black 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 on graphene and 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.

Story Source:

The above story is reprinted (with editorial adaptations by ScienceDaily staff) from materials provided by DOE/Pacific Northwest National Laboratory.

Journal Reference:

Rong Kou, Yuyan Shao, Donghai Mei, Zimin Nie, Donghai Wang, Chongmin Wang, Vilayanur V Viswanathan, Sehkyu Park, Ilhan A. Aksay, Yuehe Lin, Yong Wang, Jun Liu. Stabilization of Electrocatalytic Metal Nanoparticles at Metal-Metal Oxide-Graphene Triple Junction Points. Journal of the American Chemical Society, 2011; 110208101227051 DOI: 10.1021/ja107719u

Note: If no author is given, the source is cited instead.

Disclaimer: Views expressed in this article do not necessarily reflect those of ScienceDaily or its staff.

New technology for cheaper, more efficient solar cells

The sun provides more than enough energy for all our needs, if only we could harness it cheaply and efficiently. Solar energy could provide a clean alternative to fossil fuels, but the high cost of solar cells has been a major barrier to their widespread use.

Stanford researchers have found that adding a single layer of organic molecules to a solar cell can increase its efficiency three-fold and could lead to cheaper, more efficient solar panels. Their results were published online in ACS Nano on Feb. 7.

Professor of chemical engineering Stacey Bent first became interested in a new kind of solar technology two years ago. These solar cells used tiny particles of semiconductors called "quantum dots." Quantum dot solar cells are cheaper to produce than traditional ones, as they can be made using simple chemical reactions. But despite their promise, they lagged well behind existing solar cells in efficiency.

"I wondered if we could use our knowledge of chemistry to improve their efficiency," Bent said. If she could do that, the reduced cost of these solar cells could lead to mass adoption of the technology.

Bent discussed her research on Feb. 20, at the annual meeting of the American Association for the Advancement of Science in Washington, D.C.

In principle, quantum dot cells can reach much higher efficiency, Bent said, because of a fundamental limitation of traditional solar cells.

Solar cells work by using energy from the sun to excite electrons. The excited electrons jump from a lower energy level to a higher one, leaving behind a "hole" where the electron used to be. Solar cells use a semiconductor to pull an electron in one direction, and another material to pull the hole in the other direction. This flow of electron and hole in different directions leads to an electric current.

But it takes a certain minimum energy to fully separate the electron and the hole. The amount of energy required is specific to different materials and affects what color, or wavelength, of light the material best absorbs. Silicon is commonly used to make solar cells because the energy required to excite its electrons corresponds closely to the wavelength of visible light.

But solar cells made of a single material have a maximum efficiency of about 31 percent, a limitation of the fixed energy level they can absorb.

Quantum dot solar cells do not share this limitation and can in theory be far more efficient. The energy levels of electrons in quantum dot semiconductors depends on their size -- the smaller the quantum dot, the larger the energy needed to excite electrons to the next level.

So quantum dots can be tuned to absorb a certain wavelength of light just by changing their size. And they can be used to build more complex solar cells that have more than one size of quantum dot, allowing them to absorb multiple wavelengths of light.

Because of these advantages, Bent and her students have been investigating ways to improve the efficiency of quantum dot solar cells, along with associate Professor Michael McGehee of the department of Materials Science and Engineering.

The researchers coated a titanium dioxide semiconductor in their quantum dot solar cell with a very thin single layer of organic molecules. These molecules were self-assembling, meaning that their interactions caused them to pack together in an ordered way. The quantum dots were present at the interface of this organic layer and the semiconductor. Bent's students tried several different organic molecules in an attempt to learn which ones would most increase the efficiency of the solar cells.

But she found that the exact molecule didn't matter -- just having a single organic layer less than a nanometer thick was enough to triple the efficiency of the solar cells. "We were surprised, we thought it would be very sensitive to what we put down," said Bent.

But she said the result made sense in hindsight, and the researchers came up with a new model -- it's the length of the molecule, and not its exact nature, that matters. Molecules that are too long don't allow the quantum dots to interact well with the semiconductor.

Bent's theory is that once the sun's energy creates an electron and a hole, the thin organic layer helps keep them apart, preventing them from recombining and being wasted. The group has yet to optimize the solar cells, and they have currently achieved an efficiency of, at most, 0.4 percent. But the group can tune several aspects of the cell, and once they do, the three-fold increase caused by the organic layer would be even more significant.

Bent said the cadmium sulfide quantum dots she is currently using are not ideal for solar cells, and the group will try different materials. She said she would also try other molecules for the organic layer, and could change the design of the solar cell to try to absorb more light and produce more electrical charge. Once Bent has found a way to increase the efficiency of quantum dot solar cells, she said she hopes their lower cost will lead to wider acceptance of solar energy.

Story Source:

The above story is reprinted (with editorial adaptations by ScienceDaily staff) from materials provided by Stanford University, via EurekAlert!, a service of AAAS.

Journal Reference:

Pendar Ardalan, Thomas P. Brennan, Han-Bo-Ram Lee, Jonathan R. Bakke, I-Kang Ding, Michael D. McGehee, Stacey F. Bent. Effects of Self-Assembled Monolayers on Solid-State CdS Quantum Dot Sensitized Solar Cells. ACS Nano, 2011; : 110207102503043 DOI: 10.1021/nn103371v

Note: If no author is given, the source is cited instead.

Disclaimer: Views expressed in this article do not necessarily reflect those of ScienceDaily or its staff.

'Tall order' sunlight-to-hydrogen system works, neutron analysis confirms

 Researchers at the Department of Energy's Oak Ridge National Laboratory have developed a biohybrid photoconversion system -- based on the interaction of photosynthetic plant proteins with synthetic polymers -- that can convert visible light into hydrogen fuel.

Photosynthesis, the natural process carried out by plants, algae and some bacterial species, converts sunlight energy into chemical energy and sustains much of the life on earth. Researchers have long sought inspiration from photosynthesis to develop new materials to harness the sun's energy for electricity and fuel production.

In a step toward synthetic solar conversion systems, the ORNL researchers have demonstrated and confirmed with small-angle neutron scattering analysis that light harvesting complex II (LHC-II) proteins can self-assemble with polymers into a synthetic membrane structure and produce hydrogen.

The researchers envision energy-producing photoconversion systems similar to photovoltaic cells that generate hydrogen fuel, comparable to the way plants and other photosynthetic organisms convert light to energy.

"Making a, self-repairing synthetic photoconversion system is a pretty tall order. The ability to control structure and order in these materials for self-repair is of interest because, as the system degrades, it loses its effectiveness," ORNL researcher Hugh O'Neill, of the lab's Center for Structural Molecular Biology, said.

"This is the first example of a protein altering the phase behavior of a synthetic polymer that we have found in the literature. This finding could be exploited for the introduction of self-repair mechanisms in future solar conversion systems," he said.

Small angle neutron scattering analysis performed at ORNL's High Flux Isotope Reactor (HFIR) showed that the LHC-II, when introduced into a liquid environment that contained polymers, interacted with polymers to form lamellar sheets similar to those found in natural photosynthetic membranes.

The ability of LHC-II to force the assembly of structural polymers into an ordered, layered state -- instead of languishing in an ineffectual mush -- could make possible the development of biohybrid photoconversion systems. These systems would consist of high surface area, light-collecting panes that use the proteins combined with a catalyst such as platinum to convert the sunlight into hydrogen, which could be used for fuel.

The research builds on previous ORNL investigations into the energy-conversion capabilities of platinized photosystem I complexes -- and how synthetic systems based on plant biochemistry can become part of the solution to the global energy challenge.

"We're building on the photosynthesis research to explore the development of self-assembly in biohybrid systems. The neutron studies give us direct evidence that this is occurring," O'Neill said.

The researchers confirmed the proteins' structural behavior through analysis with HFIR's Bio-SANS, a small-angle neutron scattering instrument specifically designed for analysis of biomolecular materials.

"Cold source" neutrons, in which energy is removed by passing them through cryogenically chilled hydrogen, are ideal for studying the molecular structures of biological tissue and polymers.

The LHC-II protein for the experiment was derived from a simple source: spinach procured from a local produce section, then processed to separate the LHC-II proteins from other cellular components. Eventually, the protein could be synthetically produced and optimized to respond to light.

O'Neill said the primary role of the LHC-II protein is as a solar collector, absorbing sunlight and transferring it to the photosynthetic reaction centers, maximizing their output. "However, this study shows that LHC-II can also carry out electron transfer reactions, a role not known to occur in vivo," he said.

The research team, which came from various laboratory organizations including its Chemical Sciences Division, Neutron Scattering Sciences Division, the Center for Structural Molecular Biology and the Center for Nanophase Materials Sciences, consisted of O'Neill, William T. Heller, and Kunlun Hong, all of ORNL; Dimitry Smolensky of the University of Tennessee; and Mateus Cardoso, a former postdoctoral researcher at ORNL now of the Laboratio Nacional de Luz Sincrotron in Brazil.

"That's one of the nice things about working at a national laboratory. Expertise is available from a variety of organizations," O'Neill said.

The work, published in the journal Energy & Environmental Science, was supported with Laboratory-Directed Research and Development funding. HFIR is supported by the DOE Office of Science.

Story Source:

The above story is reprinted (with editorial adaptations by ScienceDaily staff) from materials provided by DOE/Oak Ridge National Laboratory.

Journal Reference:

Mateus B. Cardoso, Dmitriy Smolensky, William T. Heller, Kunlun Hong, Hugh O'Neill. Supramolecular assembly of biohybrid photoconversion systems. Energy & Environmental Science, 2011; 4 (1): 181 DOI: 10.1039/C0EE00369G

Note: If no author is given, the source is cited instead.

Disclaimer: Views expressed in this article do not necessarily reflect those of ScienceDaily or its staff.

New method for unraveling molecular structures

Chemists at the Karlsruhe Institute of Technology (KIT) and the Technische Universitaet Muenchen (TUM) introduced a new method for identifying chemical compounds. The approach they used is an improvement on nuclear magnetic resonance (NMR) measurements -- for decades one of the most successful methods for determining the chemical structure of organic molecules.

The results now published in the scientific journal Angewandte Chemie show a sophisticated approach to structural data when classical methods of analysis fail.

The team of Professor Burkhard Luy from KIT and Junior Professor Stefan F. Kirsch from the TUM has now shown for the first time that certain NMR parameters, the so-called residual dipolar couplings (RDCs), can make a significant contribution towards determining the constitution of chemical compounds when traditional methods fail. To do this they embedded molecules of the compound in a gel which slightly constricts their mobility. By stretching the gel, the molecules can be aligned along a preferred orientation. While residual dipolar couplings average out in solution, they become measurable in such partially aligned samples and provide valuable structural information that can be used to build a model of the molecule.

To test this new approach to chemical structure determination the scientists examined a molecule whose atomic composition was known, but not the precise connectivities of the individual atoms in the molecule. The molecule was obtained using a unique reaction, so there were no precedents for its structure. Classical methods of analysis failed because of the compactness of the molecule. In this particular case it was only possible to determine the structure by means of residual dipolar couplings, so that the newly acquired knowledge could be used to draw conclusions about the formation of the molecule -- something that in the past could only be speculated about.

"This type of analysis will not be suitable for all structures in the future," said scientists Luy and Kirsch. "There will still be molecules whose structures will defy all attempts at unraveling, in spite of tremendous efforts and cutting-edge technologies. But this new method provides us with one further tool to help us unravel the structural mysteries of nature."

This research was funded through the German Research Foundation DFG (Heisenberg Program, Research Group FOR 934) and the Chemical Industry Fund. The scientists conducted their measurements on equipment from the Bavarian NMR Center.

Story Source:

The above story is reprinted (with editorial adaptations by ScienceDaily staff) from materials provided by Karlsruhe Institute of Technology.

Journal Reference:

Grit Kummerlöwe, Benedikt Crone; Manuel Kretschmer, Stefan F. Kirsch and Burkhard Luy. Residual Dipolar Couplings as a Powerful Tool for Constitutional Analysis: The Unexpected Formation of Tricyclic Compounds. Angewandte Chemie International Edition, 2011; DOI: 10.1002/anie.2010007305

Note: If no author is given, the source is cited instead.

Disclaimer: Views expressed in this article do not necessarily reflect those of ScienceDaily or its staff.