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The crystal structure of the nanoporous crystal showing the ‘molecular wall-tie’ ligands (green) binding between the iron centres

Abstract:
Scientists are a step closer to being able to prepare porous solids that can mimic the sophisticated chemistry found in nature thanks to new research involving Cardiff University.

Revolutionising industrial catalysts

Wales | Posted on April 19th, 2010

Researchers from the University's School of Chemistry and the University of Manchester have succeeded in engineering crystals that are able to maintain their structure, providing a permanent porous matrix within which chemical reactions can take place. Their findings are published in the journal Science.

With this new porous crystal, made from an iron-containing compound called phthalocyanine, the group are looking to nature to maximise its potential within the field of industrial catalysts.

They are taking their initiative from enzymes - nature's catalysts that have a wide range of roles in biological environments, including speeding up chemical reactions within the human body. The research team are particularly interested in hemoproteins, a type of protein that is unusual in the diversity of tasks they are able to perform.

Lead author on the paper, Professor Neil McKeown, School of Chemistry, explains the significance of the group's achievement: "Normally the voids within nanoporous crystals of this type need to be filled with organic solvent and if this is removed they simply collapse losing their porosity and therefore the space in which to carry out chemical reactions. But by taking inspiration from the use of cavity wall-ties in architectural engineering, we have stabilised our crystals with the addition of suitable ligands, that can bind simultaneously to two iron atoms, thus acting as ‘molecular wall-ties."

The design of the new type of crystal is such that they can exist happily in water based environments and are accessible to gas molecules. This aspect makes them a contender for future industrial catalysts.

The group used the Science and Technology Facilities Council's Daresbury Laboratory and Diamond's Single Crystal Diffraction beamline I19 to understand whether it is possible to make porous crystals with the reactivity of hemoproteins in order to produce more effective man-made catalysts.

This research was funded by the Engineering and Physical Sciences Research Council (EPSRC). The full article ‘Heme-Like Coordination Chemistry Within Nanoporous Molecular Crystals' C. Grazia Bezzu, Madeleine Helliwell, John E. Warren, David R. Allan, Neil B. McKeown, is published in Science and available online here: www.sciencemag.org/cgi/content/abstract/327/5973/1627

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