Synthetic molecular sieve binds water better than zeolites
James E. Kloeppel, Physical Sciences Editor
CHAMPAIGN, Ill. — Zeolites are an extremely important class
of inorganic
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| Photo courtesy M.E. Kosal and K. Suslick |
| Space-filling model of the structure of a molecularly
built molecular sieve. |
materials that can separate gases or liquids on the basis of molecular
size and shape. The backbone of a billion-dollar-a-year industry,
these molecular sieves are used in numerous applications, from the
production of biodegradable detergents, to the removal of moisture
from natural gas pipelines, to the catalytic cracking of
heavy petroleum distillates into gasoline.
Now, chemist Kenneth S. Suslick and colleagues at the University
of Illinois at Urbana-Champaign have created a new class of materials
that are like zeolites in many ways. These new molecular solids
are more than 50 percent empty space space that can trap molecules
of the right size and shape, including water. The scientists report
their discovery in a paper that has been accepted for publication
in the journal Nature Materials, and posted on its Web site www.nature.com/materials.
"This organic zeolite analogue binds water faster and more
strongly than the best drying agents and has a higher capacity for
storing water," said Suslick, a William H. and Janet Lycan
Professor of Chemistry at Illinois. "The material also shows
shape selectivity, permitting only a narrow range of molecules to
enter."
A naturally occurring mineral consisting of aluminum and silicon,
zeolites were discovered in the Middle Ages. At the time, the properties
of a material were tested by heating it with a blowpipe. When this
material was heated, boiling water was released. The name zeolite
is derived from Greek words meaning "boiling stone."
The ability to make other kinds of molecular sieves has been a
major goal in materials chemistry. That goal has been frustrated,
however, because most solids are not porous to begin with, and the
process of generating pores causes most materials to collapse.
To build robust nanoporous solids that are not based on silica
and alumina, the researchers used much larger molecular building
blocks called metalloporphyrins doughnut-shaped molecules
that bind metal atoms in the middle hole. Metalloporphyrins are
closely related to hemoglobin (the red pigment in blood) and chlorophyll
(the green pigment in plants).
By heating a mixture of a special porphyrin acid and cobalt chloride
to 200 degrees Celsius, Suslick and his colleagues created a compound
called PIZA-1 (Porphyrinic Illinois Zeolite Analogue #1).
"PIZA-1 demonstrated remarkable properties as a synthetic
molecular sieve for removing water from common organic solvents,"
Suslick said. "In addition, because the metalloporphyrin has
a metal in the middle that can be catalytically active, the potential
exists to make shape-selective catalysts for specific purposes.
Not only can we selectively absorb molecules into the solid, we
can also make the trapped molecules undergo chemical reactions
such as the catalytic oxidation of fuels."
Catalytic reactions that would convert the hydrocarbons in gasoline
into the chemicals that react to make polymers such as nylon are
not yet possible to achieve, Suslick said. "But the ability
to use fossil fuels as chemical feedstocks, rather than just burning
them, is a technology that will become very important this century."
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