of Washington, Seattle, is one of the most

imaginative people in the community.

any chemists strive to be grand

architects, building imposing molecular edifices with dozens or even
hundreds of atoms, bonds twisting
this way and that. Not Roy Periana.
He has spent his career focused on
just one bond, a link between a carbon and a
hydrogen atom in a molecule of methane, the
main component of natural gas. You might
say its kind of sad, Periana says, chuckling.
But if I can control the reactivity of this one
bond, I can change the world.
Hes getting close. Working with colleagues
at the Scripps Research Institute in Jupiter,
Florida, Periana has come up with a new
way to tweak this bond. If he can perfect
his technique, it would give chemists a
cheap, efficient way to convert natural gas
to methanol and other key starter materials
for the petrochemical industrymaterials
that can then be turned into liquid fuels
and commodity chemicals. Its a simple
change that could have profound effects
especially as the shale drilling boom provides
abundant new supplies of natural gas. It
could upend the petrochemical industry, the
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worlds largest economic enterprise, because

it would allow the industry to rely on gas
rather than oil. It could also profoundly
alter global energy security, by providing
gas-rich nations with a way to break their
dependence on imported oil. The potential
financial impact, Periana notes, is enormous:
Youre looking at a gazillion dollars.
Given such weighty implications, its not
surprising that chemists have been trying to
orchestrate the methane transformation for
decades, mostly by using catalysts that can
cause the reaction without being consumed
themselves. This has been one of the holy
grails of catalysis, says George Huber, a
chemist at the University of Wisconsin,
Madison. But to date, the methods have been
balky or too expensive.
Thats where Perianas approach comes
in. Hes using a different set of would-be
catalystscheap, abundant metalsplus
some extra chemical tricks to convert
methane to methanol at low temperatures.
But his team still faces major technical
obstaclesand some critics suggest Periana
is prone to premature hype. Still, many
researchers are watching closely. Roy, says
James Mayer, a chemist at the University

MY WHOLE VISION was to be a scientist,

says Periana, who is 57. But he grew up in the

small capital city of Georgetown in what was
then British Guiananow Guyanain South
America. His school had meager science facilities, and Periana spent countless hours
in the citys public library, alone with musty,
outdated encyclopedias and textbooks. He
taught himself how to build a telescope using his grandfathers glasses, constructed his
own Bunsen burner, and, of course, synthesized every type of explosive a teenage boy
could desire. The pivotal moment was reading a book that said if you could invent a
machine that duplicated photosynthesis, you
could feed an entire city, Periana recalls. I
knew then I was going to be an inventor.
Perianas father, a photographer, befriended a U.S. diplomat, who helped secure
a U.S. residence permit for Roy. Periana
studied at the University of Michigan, Ann
Arbor, and ultimately earned his Ph.D. at
the University of California (UC), Berkeley,
in 1985. There he discovered the problem
hes been trying to solve ever since: finding
a cheaper, better way to transform gaseous
methanea member of a large class of
molecules known as hydrocarbonsinto
liquid chemical feedstocks.
The conventional way of producing those
feedstocks starts with crude oil, a collection
of liquid hydrocarbon molecules that are far
sciencemag.org SCIENCE

27 JUNE 2014 VOL 344 ISSUE 6191

Published by AAAS

PHOTO: MAGGIE STEBER

By transforming methane, chemist Roy Periana aims to

turn natural gas into cheap feedstocks for chemical firms
By Robert Service

Downloaded from www.sciencemag.org on October 8, 2014

The bond breaker

G A S R E V O LU T I O N

larger than methane. Chemical engineers

first distill out midsize hydrocarbons. Then,
they use heat and catalytic minerals to break
apart the larger heavy hydrocarbons, in a
process known as cracking.
An alternative approach starts with much
smaller hydrocarbons, such as the methane,
ethane, and propane in natural gas. Chemists
then try to stitch them together to form larger,
liquid hydrocarbons. The challenge is the
way methane is put together. The molecule
consists of one carbon atom surrounded by
four hydrogen atoms (CH4). Each hydrogen
shares two electrons with the central carbon,
an extremely stable configuration that makes
the atoms unwilling to react.
One way to trigger a reaction is to
ignite methane. The heat gives methanes
carbon atom enough energy to shake free
from its hydrogens and react with oxygen.
Unfortunately, burning methane obliterates
all of its C-H bonds, converting the
hydrocarbon to CO2 and heat. Thats nice if
you want to heat your house, but not if you
want to make liquid fuels.
Nearly a century ago, chemists came
up with molecular knitting technologies
that leave some of methanes bonds intact.
But they are too expensive for most uses
because they require relatively high
temperatures (between 800C and 900C)
and costly facilities. (The cost is one reason
oil companies each year burn off roughly
$40 billion worth of natural gas recovered
with oil.)
In the 1970s and 1980s, some researchers
thought theyd found a better solution.
They discovered that when lithium and a
few other metals were paired with oxygen,
they would form catalysts that broke those
C-H bonds without so much heat, and some
even produced small amounts of methanol.
But the catalysts were so hungry for C-H
bonds that they cannibalized the methanol
as fast as it was created. So, after decades of
frustration, most researchers gave up. We
ran out of ideas, says George Whitesides, a
chemist at Harvard University.

PHOTO: MAGGIE STEBER

EARLY ON, Periana realized that the failed

cannibal catalysts had something in common. They worked by generating other compounds that were radicals in chemistry
lingo, meaning they have a lone electron in
one orbital around the nucleus. That makes
the radical eager to either gobble up an additional electron to fill the orbital or cough
one out to empty the orbital.
Periana thought a less radical approach
might work better. While at UC Berkeley,
he helped discover catalysts that didnt use
radicals to split C-H bonds in hydrocarbons.
But these catalysts, which belong to a part of
the periodic table called transition metals,

were too fragile and expensive for industrial

use. In 1993, while working in California
at Catalytica Inc., he and his colleagues
developed a potentially practical catalyst
that also split the bonds, this time based on
mercury 2+ (Hg2+). On the periodic table,
Hg2+ is next to a cheaper, more abundant
class of metals known as main group metals.
Again, however, difficulties jacked up the
cost; in particular, the team couldnt figure
out how to get around a problem involving
excess water, which stalled the reaction by
quenching the catalysts thirst for electrons.
So he circled back to other transition metals,
spending decades on essentially fruitless
experiments. We were stuck, Periana says.
Until last year, when his lab again shifted
course to work on thallium (Tl), lead (Pb),
and other more abundant main group
metals. To their surprise, they found that Tl3+

SPECIAL S ECTION

Perianas team still faces a thorny problem,

however: Thallium ions wind up with two
extra electrons that must be stripped off to
start the cycle anew. To make that process
economical, the chemists cant use expensive
compounds. Instead, theyll likely need to
use just oxygen from air, but have yet to
demonstrate that they can do it.
As a result, most chemists are reluctant
to call the Periana labs findings a true
breakthrough. Its still a long way from
something that is practical, says John
Hartwig, a hydrocarbon chemist at UC
Berkeley. Privately, others go further,
arguing that Periana routinely overstates his
findings, making it sound like they will soon
revolutionize the petrochemical business.
With Roy there tends to be more hand
waving and less deliverable on the ground
says one U.S.-based chemist.

To be successful, Perianas team will need to scale up their laboratory experiments.

and Pb4+ generated methanoleven in the

presence of the water that had stalled the
earlier mercury catalyst. Then the eureka
moment hit us, Periana says.
The key insight, he says, involved
something called the water exchange rate
constant. It refers to the fact that atoms
dont bond in the static way we typically
imagine. Instead, they are more like the
shifting partners at a swirling square dance
than couples at a formal ball who never
separate. And it turns out that different
metals exchange their water partners at
vastly different rates. Thalliums trading rate,
for example, is 19 orders of magnitude higher
than platinums.
Such speed dating presents thallium with
plenty of opportunities to chass up to a
methane molecule and snag a pair of electrons
from a C-H bond. And in the presence of
acetic acid and other solvents, the thallium
connects whats left of the methane to a
molecule in the solvent, creating an alcohol
ester. Add water, and you get methanol and
more acetic acid.

SCIENCE sciencemag.org

That said, many outsiders think Perianas

scheme just might work. The new insights
into metal catalysts are really important,
says Harvards Whitesides, and whenever
you open the door to a new possible class of
reactions, people will take advantage of it.
Perianas team believes it has a solution to
the extra electrons. In the 1960s, researchers
developed a broad literature on using oxygen
in air to snatch electrons from copper, in a
process used to make a commodity chemical
called acetaldehyde. A similar process will
enable them to economically tap air to
fuel the metal catalysts, predicts Michael
Konnick, a research chemist in Perianas
group. I have no doubt, he says, that the
laws of the universe say it can be done.
It appears that some venture capitalists
agree. Periana says hes already seen interest
from investment firms and large chemical
companies in starting a company to develop
the technology. If it works, Periana will
finally achieve his goal of cheaply tweaking
his favorite chemical bond, and just maybe
change the world in the process.
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