Nanoscale 'Goldilocks' phenomenon could improve biofuel production

Jan 16, 2013 by Jared Sagoff
A computer graphic showing a fructose molecule (white, gray and red chain-like structure) within a zirconium oxide nanobowl (at center). Other nanobowls in the array are unoccupied. The red atoms are surface oxygen and the blue atoms are zirconium. Click on the image to view a larger version. Credit: Larry Curtiss, Argonne National Laboratory

(Phys.org)—In a case of the Goldilocks story retold at the molecular level, scientists at the U.S. Department of Energy's (DOE) Argonne National Laboratory and Northwestern University have discovered a new path to the development of more stable and efficient catalysts.

The research team sought to create "nanobowls" – nanosized bowl shapes that allow inorganic catalysts to operate selectively on particular molecules.

Catalysts are vitally important substances that enable the production of everything from petroleum to soap. In 2009, Argonne and Northwestern, along with the University of Wisconsin at Madison and Purdue University, jointly founded the Institute for Atom-Efficient (IACT) to research new catalyst designs to improve the efficiency of producing fuels from biomass. IACT is one of the Energy Frontier Research Centers funded by DOE's Office of Science to accelerate research toward meeting our critical energy challenges.

"Nanobowls are intended to mimic the selective enzymes found in nature," said Argonne chemist Jeffrey Elam. "We can tailor the nanobowl size and shape to accept certain molecules and reject others."

Although nanobowls and enzymes both use a lock-and-key mechanism, they serve different purposes and operate in dramatically different environments. "Enzymes are composed of organic materials suitable for the relatively low-temperature, low-pressure environments of ," Elam said. "But the extremely necessary for biomass conversion would cause the enzyme proteins to unravel. In contrast, the nanobowls are inorganic, and this makes them very durable."

According to Elam, the design's effectiveness correlates with the size and depth of the bowl; if the bowl is too large or shallow, practically any molecule can access the catalyst, which can lead to uncontrolled and often undesirable side reactions. Likewise, if the bowl is too small or deep, even the intended molecule will not fit into the bowl. However, if the nanobowl structure is "just right," only the intended molecule will reach the catalyst and react.

The trick to building a nanobowl with a specific shape and depth is to use a nano-sized template. In the first proof-of-concept nanobowl experiments, bulky organic molecules called calixarenes were used as the template. They were grafted onto a titanium dioxide surface that served as both the catalyst and the "table" for the nanobowl to rest on. Next, the walls of the bowl were built around the template, one atomic layer at a time, using atomic layer deposition (ALD), a technology borrowed from the semiconductor industry. Once the scientists grew the nanobowl to the proper height, they burned away the organic template, leaving behind a cavity with the same shape.

Since the titanium dioxide is in the form of a nanopowder with lots of surface area, the experiment required the scientists to create millions of these nanobowls. Fortunately, the processing techniques that Elam and his colleagues employed can be scaled up so that successful nanobowls identified in these bench-scale studies can eventually have a real-world impact.

The next step, Elam said, involves applying the knowledge gained in these studies to make nanobowl catalysts tailored for biofuel production. "The overarching problem in these reactions is to selectively remove oxygen without breaking carbon-carbon bonds."

Elam and his colleagues also used the 12ID-C X-ray beamline at the laboratory's Advanced Photon Source to characterize the structure of the nanobowls.

The work was reported in the journal Nature Chemistry.

Explore further: New process can convert human-generated waste into fuel in space

Related Stories

Putting the 'fuel' in biofuels

May 27, 2011

(PhysOrg.com) -- Recent discussions of methods by which biomass -- grasses, trees, and other vegetation -- could be turned into fuel makes a lot of sense in theory. Plant matter is composed of energy-intensive ...

New Class of Catalyst Sports Shapely Selectivity

Mar 10, 2010

A new class of catalytic material has been studied by scientists at Pacific Northwest National Laboratory. Metal-organic frameworks (MOFs) display a unique three-dimensional structure that is highly selective ...

Recommended for you

Electronic switches on the molecular scale

Nov 25, 2014

A molecular electronic switch is a junction created from individual molecules that can alternate between two or more stable states, making the switch act as a conductor or an insulator. These switches show ...

Mimicking photosynthesis with man-made leaves

Nov 25, 2014

Scientists have long been trying to emulate the way in which plants harvest energy from the sun through photosynthesis. Plants are able to absorb photons from even weak sunlight using light antennae made ...

User comments : 1

Adjust slider to filter visible comments by rank

Display comments: newest first

jibbles
not rated yet Jan 17, 2013
wow nice work

Please sign in to add a comment. Registration is free, and takes less than a minute. Read more

Click here to reset your password.
Sign in to get notified via email when new comments are made.