FALL 2006

Volume 7 Number 1

Research at the University of Virginia School of Engineering and Applied Science

Sustainable Energy
an Atom at a Time

Catalyzing

IMPACT

Engineering on the Move at U.Va.

The effect of this growing momentum can be seen in this issue of IMPACT. We focus on research under way to develop more efficient fuel cells as well as renewable sources of fuels and chemical intermediates. Our efforts to help our country reduce its energy dependence, however, are broadly based, including pioneering work on long-lasting and corrosion-resistant materials like amorphous metals and finding more efficient tools for medical research in the terahertz spectrum. Taken together, these articles provide a cross section of the variety and quality of research being conducted at U.Va.

By any measure, research at the School of Engineering and Applied Science is thriving. In the last two years, close to 70 percent of our research proposals have been accepted, far outstripping the National Science Foundation average, and we are well on our way to meeting our goal of doubling external research funding in the next five years. We now field first-class groups of researchers in such fields as photonics, spintronics, corrosion, biomedical engineering, software engineering, distributed systems, terahertz technology and amorphous materials, to name just a few. The University stands fully behind our efforts to strengthen our programs. It has committed to adding 25 additional faculty members over the next five years and another 25 faculty members in the five years after that. We also envision adding more than 400 students to our graduate program.

U.Va. School of Engineering and Applied Science

Barry W. Johnson Associate Dean for Research

The Road to Biodiesel

1 4

THIS ISSUE

The Elements of Catalysis

Fuel Cells in the Basement

Photography Tom Cogill

A Revolution in Metallurgy  e Terahertz Window Th on the World

Writer and Editor Charlie Feigenoff

IMPACT is published by the University of Virginia School of Engineering and Applied Science. An online version of the magazine is available at www.seas.virginia.edu/impact. Address corrections should be sent to the University of Virginia Engineering Foundation, P.O. Box 400256, Charlottesville, VA 22904-4256, or call 434.924.3072.

Graphic Design William J. Green & Associates

sustainable Research sustainable energy/Breakthrough energy

The Elements of Catalysis

Every high school chemistry student learns the definition of a catalyst, yet even the most sophisticated chemists lack a clear understanding of how catalyst surfaces work on a molecular level. Matthew Neurock, the Alice M. and Guy A. Wilson Professor of Chemical Engineering, is developing and applying quantum mechanical methods and computer simulations to understand the atomic features and molecular phenomena that govern catalysis. We are compiling a suite of tools that enable us to understand adsorbate-surface interactions and quantify the energetics of elementary reaction steps, Neurock says. This information is used to simulate the vast array of competing elementary surface reaction steps, follow the temporal surface structure and model material performance. Fuel Cells on a Budget One area in which Neurocks expertise is critical is the development of fuel cells. With support from a Multidisciplinary University Research Initiative (MURI) grant from the U.S. Army Research Office, he is part of a team developing better catalytic materials for polymer electrolyte membrane (PEM) fuel cells driven by methanol. Currently, the catalysts of choice for anodes and cathodes in the direct methanol fuel cell are platinum-based alloys, but the military would like to reduce their cost and improve their durability. They have asked the MURI team to propose novel alloys that would decrease the amount of platinum or completely replace it, increase the catalytic activity at the anode and the cathode and prevent the loss of catalyst over time. These same issues apply to hydrogen PEM fuel cells targeted

 We can calculate the kinetics of each reaction at the quantum level and then move up to the molecular scale to describe how catalysis happens on the surface.

for the automotive industry; any improvements to the catalysts for direct methanol will likely aid the hydrogen fuel cell. We can calculate the kinetics of each reaction at the quantum level and then move up to the molecular scale to describe how catalysis happens on the surface, Neurock says. With this information in hand, we can alter the alloy composition and surface structure to control the reaction to our specifications. The Three-Metal Solution Through modeling and simulation, Neurock has proposed a series of three-metal systems currently being tested by industry that provide desirable characteristics. Armed with a more exact knowledge of the sequence of methanol reactions, he and his colleagues are also exploring the use of other substances, such as hydrogen, formic acid and ethanol, as potential fuels for both portable and automotive PEM fuel cells.

IMPACT

The Road to Biodiesel

Despite all the hoopla, the nations fleet of trucks and buses will not be pulling up to their local fast food joint and filling up with a tankful of kitchen grease anytime soon. That would require retrofitting the millions of diesel-fueled vehicles currently on the road. The vegetable oils and animal fats used in cooking are composed of triglycerides, which could clog conventional diesel systems. For biodiesel to gain acceptance, it must have flow properties similar to ordinary diesel fuel, says Professor Robert Davis, chair of the Department of Chemical Engineering. Conventional liquid catalysts now used to convert heavy fats and oils to thinner biodiesel must be neutralized at the end of the process and disposed of. With funding from the U.S. Department of Energy, Davis is focusing on developing solid catalysts that would be recoverable and reusable, making biodiesel more attractive economically and environmentally. Liquid catalysts do have one important advantage in the production of biodiesel: they can be mixed easily and thoroughly with triglycerides. To duplicate this effect, Davis solid catalyst will be highly porous. He is using nanodesign techniques to optimize these pores so that the triglycerides receive maximum exposure to the catalytic agents. Even in his most optimistic moments, Davis doesnt imagine that the United States could produce enough biodiesel to replace all the diesel fuel it now consumes. In his view, a more likely future for biodiesel is as a renewable fuel additive for conventional diesel engines. Biodiesel restores the lubricating qualities removed in the process of formulating lowsulfur, low-polluting fuel. But even if it is manufactured in sufficient quantities to serve as a fuel additive, processing biodiesel creates another challenge the production of significant amounts of glycerol as a byproduct. For every three

molecules of biodiesel, we create a molecule of glycerol, he observes. If we start producing biodiesel on a large scale, the amount of glycerol were going to have on hand is going to add up quickly. Rather than dispose of the glycerol, Davis wants to devise a process that transforms it into useful chemicals and here again he is breaking new ground. Most organic chemical products use oil and natural gas as feedstock, Davis explains. To make high-value chemicals from hydrocarbons, you add oxygen

 To process biomolecules on an industrial scale, you need new techniques, new catalysts and new strategies.

and increase their complexity. Glycerol and other biomolecules are rich in oxygen to begin with, so the process of transforming them into useful feedstock requires chemists to reduce them, effectively removing some of the oxygen. In addition, petrochemical production is often done in the gas phase. Biomolecules are soluble in water, so a more appropriate approach would be to immerse them in an aqueous environment. To process biomolecules on an industrial scale, you need new techniques, new

catalysts and new strategies, says Davis. With funding from the National Science Foundation, Davis is developing fundamental tools to study and manipulate the behavior of different catalysts in aqueous environments. In essence, were learning how to convert sugars into the stuff of everyday life, he says.

Erin Maris The bucking High-Carb is a trend. Diet For more than a century, chemists have been perfecting the process of transforming hydrocarbons into chemicals like ethylene and propylene glycol, the building blocks of modern life. Maris would like to be part of a movement that produces the same substances using renewable resources like sugars.

Before this can be done, these sugar-based reactions have to be studied in detail. In conjunction with adviser Robert Davis, Maris is investigating catalytic reactions that transform sorbitol into glycol. Im trying to decouple reactions that occur in solution and those that occur on the surface of the catalyst, she says. We add a base to promote the reaction rate, and I am trying to determine if there is a relationship

between the hydroxyl and the surface of the metal we use as a catalyst. Maris has presented her work at a number of conferences. Were encouraged to make presentations, she says. Its a great way to gain exposure and be exposed to new ideas at the same time.

IMPACT

Fuel Cells in the Basement

Fuel cells have been touted as the environmentally sound replacement for everything from AAA batteries to the massive steam turbines that run our power plants. The type of fuel cell that has received the most attention in recent years is one that uses hydrogen as a fuel. Hydrogen fuel cells are exceptionally clean, producing nothing but water and heat as byproducts, but theres a rub. engineer Steven McIntosh observes, The hydrogen economy will be a long time coming. The Solid Oxide Alternative McIntosh himself focuses on solid oxide fuel cells that can use any combustible fuel, including gasoline, diesel and biofuels. Because they take advantage of existing infrastructure, solid oxide fuel cells will give us the ability to realize the potential of fuel cells in the near future, he says. McIntosh is working to find high-performance anode materials that provide the ideal balance of catalysis and conductivity. The requirements for these materials are especially stringent, as solid oxide fuel cells require temperatures of over 700 degrees Celsius to operate; in addition, the ideal anode would suppress the formation of carbon, which is a byproduct of transforming hydrocarbons into electricity. better understand their properties. We know that if you pull oxygen out of these materials, you improve the conductivity, he says, but we are still trying to understand the limiting factors. One of McIntoshs graduate students, Michael van den Bossche (09), is characterizing the effectiveness of a lanthanumchromium-strontium-manganeseoxide anode for solid oxide fuel cells powered by methane. He is varying the proportion of elements, conducting the reaction at different temperatures and varying the oxygen content to determine the effects of these changes on the ratio of carbon monoxide to carbon dioxide produced. In McIntoshs view, solid oxide fuel cells would be ideal for home use and distributed power generation. Because they could be used to generate heat as well as electricity, they are more efficient than traditional energy sources and they would be considerably more versatile since they are not limited to a single kind of fuel, he says.

 The hydrogen economy will be a long time coming.

Most commercially available hydrogen is produced from hydrocarbons by an energyconsuming process, which also produces carbon dioxide, a greenhouse gas. Storing and distributing this highly flammable gas is also problematic. As chemical

An Anode Library McIntoshs approach is to develop a library of possible mixed oxide materials that may prove useful as an anode and subject each of them to a series of tests that help him

A Revolution in Metallurgy
More than 20 years ago, physicist Joseph Poon was searching for a book at the U.Va. library, only to find that materials scientist Gary Shiflet had already taken it out. Poon tracked Shiflet down, and the two men found that they shared other interests as well particularly the nascent field of amorphous metals. Thus began an extremely productive, longterm collaboration that led, three years later, to the introduction of amorphous aluminum and that has systematically enlarged our understanding of the basic properties of these new materials. When we started out, amorphous metals were a university curiosity, recalls Shiflet. Now groups like the Defense Advanced Research Projects Agency (DARPA) recognize its potential. And with good reason: amorphous metals can be considered the most significant advance in metallurgy in thousands of years. Amorphous metals are cooled so quickly that crystals do not have a chance to form, and their constituent atoms are arranged randomly. Without crystalline boundaries, these materials approach their theoretical strength and hardness, they exhibit excellent corrosion resistance and, since they are essentially frozen liquids, they can be easily molded like plastic. A Productive Partnership Shiflet and Poon share program management duties. Shiflet leads the effort to develop extremely light, aluminum-based metals for transportation and aerospace, while Poon takes the lead in discovering new kinds of amorphous steel for naval applications. Although the focus of these projects is different, they work together closely, sharing research support equally and using many of the same methods. For instance, they both employ atomistic modeling as well as theoretical studies to learn more about how atoms interact to retain the liquid structure. Once you have the science firmly in place, you can be predictive, says Shiflet. This knowledge was critically important in overcoming the first challenge to acceptance of amorphous metals an inability to produce them in bulk form. In order to cool the molten alloy quickly enough to prevent crystal formation, it had to be kept very thin, a factor that had limited the application of amorphous metals to coatings. Shiflet and Poon played an important role in creating liquid metals that are thick enough to be used for structural purposes. Taking on the Next Challenge Currently, they are working to improve its ductility. Like glass, amorphous metals tend to shatter, rather than absorb punishment. The key, Shiflet says, is finding out on an atomistic level where the ductility is coming from. We realize that atoms are not just packing materials, but that electron activity is important as well. With support from DARPA, they have assembled a team that includes other researchers from U.Va. as well as from Case Western Reserve, Georgia Tech and Carnegie Mellon to work on this project.

The Terahertz Window on the World

The terahertz spectrum, wedged between the infrared wavelengths and microwave, used to be terra incognita, but no more. For years, there were few good sources and detectors in this frequency range, Research Associate Professor Tatiana Globus explains. But this situation has changed dramatically in the last five years, thanks in part to pioneering work done at U.Va. This opens the way for a wide range of exciting applications. The Next Tool for Medical Research Terahertz radiation is particularly useful for detecting small molecules, like carbon monoxide, ozone and water in the gas phase, that absorb terahertz radiation and resonate in the terahertz. It is also useful for characterizing weak chemical bonds in big molecules, an area where established technologies like infrared spectroscopy have limitations. The specific resonance frequency of biomolecules in the terahertz can be used as a signature, helping us identify biological threats, Globus says. Globus is contributing her expertise in spectroscopy to a group led by Professor Don Brown, chair of the Department of Systems and Information Engineering, that has received a W. M. Keck Foundation grant to develop a device using the terahertz spectrum to study biological molecules. This technology will be particularly useful for medical research, helping us to further understand such issues as biomolecular interactions, she says. At the Frontier of Discovery From Globus point of view, the potential applications are both exciting and virtually limitless. The terahertz has been uncharted territory, she says. One of my goals is to acquaint as many young researchers with the field as possible, so that together we can start filling in the map as quickly as we can.

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