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amid a tangle of wires and plastic tubing, Morgan Mihok examines
a murky orange concoction, her thin frame hunched over to get a
better look at what she hopes is the secret to cheaper, cleaner
fuel. The vial is capped with an air-tight rubber stopper. Two long
needles connected to plastic tubes penetrate the seal, allowing
a constant flow of argon gas to purge all traces of atmospheric
air from the vial. Mihok turns on a magnetic plate beneath the test
tube, and in response a small magnet in the solution causes the
orange liquid to swirl like a mini-maelstrom. Flipping another switch,
she engages a pure blue light source. The glass of the test tube
glows sapphire, and Mihok, a second-year chemistry student, waits.
She has been preparing this experiment for weeks.
Hours of studying, meticulous note-taking, and chemical mixing are
contained in this one vial. "If everything goes right," she says
in a distracted whisper, "we should see something in 30 minutes
or so."
Mihok's experiment is based on a simple formula
plants have used for eons: water + sunlight = energy. In practical
terms, it means using sunlight to break apart the chemical bonds
between the hydrogen and oxygen atoms in water — H2O —
in order to use the elemental hydrogen for generating energy. Plants
accomplish this photosynthesis through a complex series of reactions
controlled by carbon-based enzymes. But Mihok's process is more
streamlined and entirely inorganic. In a sense, it's artificial
photosynthesis. The result — a cheap and plentiful source of
hydrogen gas — could revolutionize how machines operate. Instead
of internal combustion engines, machines of the future might be
powered by fuel cells, a type of battery that combines hydrogen
fuel and atmospheric oxygen to create electricity.
After a painfully slow half-hour, Mihok inches
closer to her glowing solution. Taking a syringe, she floods its
chamber with argon gas to eliminate all traces of air inside, pushes
the gas back out, then gently inserts the needle through the rubber
seal of the test tube and extracts some air. She rushes three feet
down the lab bench to the computer analyzer and injects the syringe
into a receptor labeled samples.
Mihok's face, calm an hour ago, looks tense. The
monitor flashes on, and a red line begins to inch its way, oh so
slowly, across the screen. Her eyes fix on that line. She points
to a spot on the screen. "That's about where the hydrogen should
show up." Nothing. The red line starts to climb. The screen blinks
— and the line is flat again. No hydrogen.
A minute later, the line starts to climb. "That's
oxygen," she says. "Some probably crept in when I took the sample,
unless there's a leak in the system, which means the whole experiment
is ruined . . . Come on, go back down." The line descends, indicating
only a small amount of oxygen. "Looks like we're going to be okay."
After another minute, the line climbs, showing that some nitrogen
has crept in too, but it appears there's no hydrogen at all.
"Chad!" Mihok calls Chad Waraksa, a graduate student
who works with her on the project, to take a look at the results.
He types a command on the keyboard and the graph changes shape.
"You have to format this for what kind of experiment you're running,"
he says. Another screen appears. Mihok jumps. "Woo hoo! Look!" Pointing
to the first line of the analysis, she reads: "Hydrogen."
he
lab Mihok and Waraksa share is one in a maze of 12 interconnected
laboratories off of an unassuming corridor in Chandlee Laboratory.
Tom Mallouk, Penn State professor of chemistry, directs the entire
wing. A sign in the hallway announces, "The Center for Miscellaneous
Chemistry: Serving Central Pennsylvania since August." The
rest of the corridor's wall space is cluttered with diagrams, displays
of published papers, and pictures of Mallouk & Co. in strange costumes
at Halloween parties. Inside the labs, where students like Mihok
and Waraksa work, counters are strewn with centrifuges, agitators,
and oscillators. Glassware and chemicals clutter the shelves. The
place sounds busy: whirs and hums and clinks muffle the students'
voices.
By
contrast, Mallouk's office at the far end of the hallway seems quiet
and orderly. High-tech micrographs share wall space with crayon
drawings done by his children and quilts stitched by his wife. A
floor-to-ceiling bin of erector set-type molecule models guards
one wall. The shelves are packed with books.
Mallouk himself is not what you'd expect in a chemist.
He's a T-shirt and blue-jeans guy, bearded and rugged, with shaggy
hair. A smile line or two betray his otherwise youthful face. His
quick wit and easy-going manner set students immediately at ease.
He's probably never been accused of being too serious.
Mallouk brought his Center for Miscellaneous Chemistry
from the University of Texas at Austin seven years ago. "I had some
colleagues at Texas who started putting signs on their doors that
read, 'The Center for Such and Such,' complete with whizbang logos,"
he explains. "They were totally serious. The funny thing is that
they were only one-man operations." Mallouk chuckles. "When the
third one went up I said, that's enough, and decided to create my
own 'center.'
"I came to Penn State for family-related reasons,"
he adds, "but also because of this university's strength in materials
research across the board. I was looking forward to collaborating
with different departments, and we're doing just that — with
electrical engineering, materials science, and physics. That's an
opportunity I probably wouldn't have had at Texas."
Mallouk has been on the trail of artificial photosynthesis
since his undergraduate days at Brown. He was in high school when
the oil embargo hit in the early 1970s and was taken with the push
for alternative fuels. "People were seriously concerned that we
were going to run out of oil and needed some other source of fuel,"
he says. "In college I got my start with a really inspiring professor
and I got to do my first real experiment — no one had ever
done it before, no directions. We were developing new kinds of semiconductor
crystals for photosynthesis reactions. That avenue of research eventually
led to a dead end, but I was hooked."
Artificial photosynthesis could provide a clean,
renewable alternative to fossil fuels: renewable because it would
require only water, clean because its only by-product would be oxygen.
What's more, the right system could produce hydrogen cheaper than
the price of gasoline — once it's running, the only energy
required is light. "There's enough energy in sunlight to vaporize
the oceans," says Mallouk. "All you need is the right catalyst."
Almost 30 years ago, a team of scientists from the
University of Tokyo took the first step toward making artificial
photosynthesis a reality. They announced in Nature that they'd successfully
split water using ultraviolet light and a catalyst of titanium dioxide.
While a system using ultraviolet light doesn't have many practical
uses (not enough ultraviolet light penetrates Earth's atmosphere),
the experiment proved that artificial photosynthesis wasn't just
a dream. Mallouk calls it proof of concept. "That paper really got
the science world in a buzz about artificial photosynthesis," says
Mallouk. "It showed us that it could be done."
About the same time, American chemists discovered
a class of compounds called ruthenium trisbipyridines that are sensitive
to blue light. These orange-colored molecules, which give Mihok's
test-tube solution its mashed Creamsicle appearance, fire off an
electron when struck by a photon of light. "Ru-bipy" — as it's
known in chemistry circles — "is a fantastic reducing agent
when stimulated by light," says Mallouk. "Water-splitting requires
1.23 volts of energy. The excited state of Ru-bipy gives off 2.1
volts — almost twice what we need."
In 1989, Japanese scientists were studying potassium
hexaniobate, a semi-conducting material made of potassium, niobium,
and oxygen. Like all semi-conductors this material can receive or
donate electrons. But unlike most, the researchers found, its many
layers can be chemically split apart into individual sheets. "The
proportions of one sheet are about the same as this," says Mallouk,
holding up a piece of notebook paper, "only on a very, very microscopic
scale. This feature is important because we've learned how to split
apart a stack of these sheets and embed pockets of catalyst between
them." More recently, British scientists discovered that another
material, iridium dioxide, is especially good at catalyzing the
production of oxygen from water, an important part of the water-splitting
process.
Artificial photosynthesis, Mallouk-style, would
work like a molecule-sized machine. When light energizes a Ru-bipy
molecule, an adjacent stack of potassium hexaniobate gladly accepts
the ejected electron and ushers it to its core, where microscopic
pockets of platinum have been implanted. "Think of the platinum
as a singles bar," explains Mihok. "It serves as a meeting place
for electrons and hydrogen ions to hook up." Hydrogen ions (protons)
are naturally present in water. And since acids, by definition,
have a higher concentration of hydrogen ions than plain water, Mallouk's
recipe calls for an acidic solution to increase the rate of the
reaction. So when an electron arrives at the platinum, it invariably
finds a waiting proton. But like many couples out on a first date,
this newly formed union doesn't like to be alone, chemically speaking,
so it finds another recently formed hydrogen atom. They bond together
and voilà: hydrogen gas.
Meanwhile, the Ru-bipy molecule is in dire need
of an electron to replace the one it ejected. If it doesn't get
another one soon, it will fall apart. Fortunately, iridium dioxide,
suspended in the mix, is an electron giver, and the ravenous Ru-bipy
snatches up an electron from the iridium dioxide molecules (only
to surrender one again when struck by another photon of light).
Soon, the iridium dioxide molecules, in turn, badly need replacement
electrons.
At this point, the only possible source of electrons
is water, and without hesitation iridium dioxide rips two electrons
from each of two adjacent water molecules. The former water molecules'
two oxygen atoms float off together as oxygen gas, and the four
remaining protons find themselves strangely drawn to a platinum
pub not far away.
In
theory, this cycle will continue until all of the water has been
photosynthetically converted to hydrogen and oxygen. "But we're
not there yet," says Mallouk. In order to develop a fully functional
water-splitting system, Mallouk's team has taken one step back,
isolating the two parts of the reaction to more closely study and
fine-tune them.
"Morgan and Chad are working on the hydrogen side,"
Mallouk explains. "They're using hydrogen iodide, which is a pretty
strong acid, as a source of protons instead of water. On the oxygen
side, we're using a chemical that gets used up to induce the reaction.
Through these methods, we've been able to experimentally demonstrate
that both sides of the reaction do what they're supposed to do."
All that remains is to put them together. Unfortunately, that's
not as easy as it sounds.
eep
in the basement of Chandlee Lab, in a dark box of a room, Chad Waraksa
blasts away at Ru-bipy molecules. "Chad's got destructive tendencies,"
jokes Mallouk. "He really likes playing with lasers." The room is
uncomfortably warm, the lighting low. Waraksa wears green-tinted
safety goggles that look like 1970s sunglasses. Beads of perspiration
dot his forehead. The room hums with electricity. Waraksa hits a
button, and a beige box the size of a small desk fires a blinding
seven-nanosecond-long pulse of emerald laser light. The bright green
blast careens through one prism, gets redirected by another, and
finally smashes into a sample of Ru-bipy. The impact of laser photons
energizes the light-sensitive molecules, setting off a torrent of
electron expulsions. A scanner that detects ultraviolet and visible
light analyzes the electron flow and sends the results to the monitor
where Waraksa sits.
"What this process does is determine the efficiency
of the light absorption of the Ru-bipy molecule," he says. Explains
Mallouk, "Efficiency has really become the focus of our research.
If every electron energized by a photon of light met up with a hydrogen
ion, then the reaction would be functioning at 100 percent efficiency.
"Right now, we're at about 3 percent. That means
3 percent of the electrons are ending up where they're supposed
to. The remaining 97 percent are probably going back where they
came from."
In order to decrease the fraction of electrons slipping
into this "back reaction," Mallouk's team has found a way to more
precisely place the platinum within the potassium hexaniobate. "Previously,
the layered potassium hexaniobate was stacked like a deck of cards,
with the platinum randomly interspersed like jokers," says Waraksa.
"But we've developed a way to slip a layer of platinum between only
two layers of potassium hexaniobate — sort of like a platinum
sandwich." The experiment that Mihok has been working on uses this
technique. The idea is that if the electron has a shorter distance
to travel to reach the platinum, it will be more attracted to a
night at the pub than to going back home.
Waraksa is also formulating another approach to
increase the reaction's effectiveness, based on an "energy gradient."
"Instead of one layer of potassium hexaniobate, I'm trying to create
three layers of different semiconductors that have an increasing
affinity for electrons," he says. "That way, each successive layer
pulls the electron further from its starting point and closer to
the platinum, making it even harder for electrons to go back."
Another side to the efficiency problem is a phenomenon
in which the rates of all the reactions are determined by the rate
of the slowest one. "They bottleneck," explains Mallouk. "Think
of a tractor-trailer going up a steep mountain road. It doesn't
matter how fast the cars behind it are, they'll all end up going
the speed of the semi. In our water-splitting system, the hydrogen
reaction takes about one millisecond, but the oxygen reaction takes
one second. That still means it's a thousand times slower than the
hydrogen reaction. But if we can shrink that difference to just
one power of ten instead of three, then we'll have a total system
efficiency of ten percent, and we'll be in business."
Despite the hurdles, Mallouk seems confident that
a working system is just a matter of time. "Well," says Mallouk
with a laugh, "Department of Energy grants run in three-year cycles,
so I hope we get our system running within the next year or so."
They won't be waiting for fireworks, either. "We're not looking
for perfection by any means. We're shooting for a few percent —
maybe ten percent would be interesting. If we demonstrate that we've
designed a reproducible method of sunlight-powered artificial photosynthesis
that works, at that moment we publish a paper — proof of concept."
That paper will ignite the field much like the first successful
artificial photosynthesis experiment did 25 years ago.
And Mallouk will be just as happy if it comes from
someone else's lab. "I don't know who will ultimately find the breakthrough
artificial photosynthesis system," he says. "It's my job to take
the science as far as it can go. When someone says to me, 'Can you
split water for me,' I see a very complex series of kinetic reactions.
But beyond cutting-edge materials and breakthrough formulas, I'm
developing good scientists. And that's the real goal. Ultimately,
even if someone else comes out with artificial photosynthesis first,
we still win."
Morgan Mihok is a chemistry major in the Eberly
College of Science and the Schreyer Honors College. Her research
adviser is Thomas Mallouk, Ph.D., the DuPont Professor of Materials
Chemistry in the Eberly College of Science, 215 Davey Lab, University
Park, PA 16802; 814-863-9673; tom@chem.psu.edu.
Chad Waraksa is a doctoral candidate in chemistry. This project
is being funded by a grant from the U. S. Department of Energy.
Andrew Gathman graduated from Penn State in May 2000 with a degree
in English. He is currently writing for Genesis Publishing in Baltimore.
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