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Two new electrolysis techniques efficiently use electricity to split carbon dioxide molecules.
CHARLES D. WINTERS/SCIENCE SOURCE

Two new ways to turn ‘garbage’ carbon dioxide into fuel

By Robert F. Service Sep. 1, 2017 , 12:15 PM

WASHINGTON, D.C.—Carbon dioxide (CO2) is society’s ultimate waste product, with

billions of tons of the stuff injected into the air every year. But recycling it into valuable
fuels and chemicals has always required too much energy to make financial sense.
Now, researchers have found two efficient ways to convert CO2 into energy-rich
byproducts, they reported last week here at a meeting of the American Chemical
Society (ACS). If they gain traction, they could help solve another pressing problem:
Because both approaches require a steady stream of electrons from a source of
electricity, they could siphon up all the “lost” solar and wind energy that can’t currently
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be stored in electric grids.

To recycle CO2, some researchers are mimicking photosynthesis, harnessing sunlight

to convert the molecule into carbohydrates. But these solar fuel reactors often need to
run at 1000°C temperatures. Other chemists favor a more traditional approach that
would carry out similar reactions, but near room temperature in electrochemical cells
that need electricity and special catalysts.

The first step in such an electrolytic approach is splitting CO2, a tough, stable molecule,
into oxygen and carbon monoxide (CO), a slightly more energy-rich molecule that can
form the basis for hydrocarbon fuels like methanol. That process starts with two
catalyst-covered electrodes dunked in a beaker of water into which CO2 has been
dissolved. The stream of electrons between these electrodes carry out separate
reactions that split water and CO2, ultimately generating CO and more water.

Theoretically, it should take just 1.33 volts of electricity—less than that produced by a
AA battery. But in practice, researchers must raise the voltage another volt or so to
drive the reaction at a faster clip. This extra voltage, known as the overpotential,
amounts to an energy surcharge that lowers the cell’s efficiency. Another problem is
that most catalysts channel more of the available electrons into splitting water rather
than converting CO2 to CO.

In 2011, researchers led by Richard Masel, a chemist and CEO of Dioxide Materials in
Boca Raton, Florida, tested a setup with silver and iridium oxide catalysts and a liquid
electrolyte to promote the CO2 to CO reaction. The electrolyte contained a compound
called imidazolium that formed a protective layer around the silver-covered electrode.
That blocked the water-splitting reaction and encouraged the catalyst to pass nearly all
its electrons to converting CO2 instead. It also produced CO with an overpotential of
just 0.17 volts. But ionic liquids can be expensive and corrosive. So Dioxide Materials
set about making a durable and cheap plastic membrane that could serve the same
function when laid atop a silver electrode.

Last year, the company reported that it had successfully made the membranes. But at
the ACS meeting, Dioxide Materials chemist Richard Ni reported that devices using
them produced CO with an efficiency nearly double that of the next best membrane. Ni
also reported that with recent upgrades, their cells can transform CO2 to CO at double
the rate of other CO2-splitting electrolyzers of a comparable size, which could help
them process large volumes of CO2 when scaled up. Ni added that the company’s
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devices remain stable and undeteriorated after 6 months of continuous operation.

“Those are very good results,” and considered good enough for a commercial product,
says Fan Shi, a chemist at the National Energy Technology Laboratory in Pittsburgh,
Pennsylvania. Dioxide Materials is not alone in trying to commercialize the process:
Already, chemical giant BASF has announced plans to produce liquid methanol fuel
using a similar method. And a German company called Sunfire announced in May that
it’s producing “blue crude,” a synthetic diesel fuel from CO2 and water using a high-
temperature process.

Meanwhile, Dioxide Materials has scaled up the size of their electrodes from squares
smaller than a U.S. postage stamp to ones bigger than an adult hand, enabling a larger
CO flux. And the company has teamed up with industrial giant 3M to produce swaths
of their imidazole membranes in a reel-to-reel process. The company is also in
discussions with industrial chemical producers like Linde and Siemens, exploring
places where they might be able to access pure CO2 waste streams and excess
renewable power. “That could be key,” Shi says. “You can store energy during periods of
low demand.”

To make a truly large-scale impact, the company may need to find cheaper electrode
catalysts than silver and iridium oxide, says Haotian Wang, a chemist at Harvard
University. Ni says the company is looking for cheaper options to replace iridium, a rare
and expensive metal.

Another long-term prospect was raised at the ACS meeting by Paul Kenis, a chemist at
the University of Illinois in Urbana. Though converting CO2 to CO is the simplest option,
Kenis and others are looking transform CO2 in one fell swoop to methane, formic acid,
methanol, or other complex hydrocarbons with more energy—and higher value. But the
reactions are more complicated, requiring not just a source of electrons but also
protons. In order to run these reactions, researchers typically use an anode to split
water molecules into protons, electrons, and oxygen, and then feed the protons and
electrons to a cathode, where they react with CO2 to make hydrocarbons. The water-
splitting reaction also normally requires a heavy energy surcharge.

At the ACS meeting, Kenis reported that his group has created a CO2-splitting device in
which they replaced the water at the anode with a liquid called glycerol, a waste
product produced by the ton in biodiesel plants. By using glycerol, Kenis says that his
team was able to reduce the overpotential in that part of their system by nearly two-
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thirds and churn out formic acid, which is widely used in chemical synthesis. Kenis
confesses that the new setup may generate side products that they don’t yet know
about and that it has a long way to go before becoming a commercial technology. But
William Goddard, a chemist at the California Institute of Technology in Pasadena, says
he was impressed with the idea. “To take what’s now considered garbage and convert
it, that has real potential,” he says.

Posted in: Chemistry

doi:10.1126/science.aap8497

Robert F. Service
Bob is a news reporter for Science in Portland, Oregon, covering chemistry, materials science, and
energy stories.
 Email Robert  Twitter

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