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Plastic that grows on trees

om fructose while leaving only traces of acid impurities. To achieve this, they experimented with a novel non-acidic catalytic system containing metal chloride catalysts in a solvent capable of dissolving cellulose.

The solvent, called an ionic liquid, enabled the metal chlorides to convert the sugars to HMF. Ionic liquids provide an additional benefit: It is reusable, thus produces none of the wastewater in other methods that convert fructose to HMF.

Metal chlorides belong to a class of ionic-liquid-soluble materials called halides, which “in general work well for converting fructose to HMF,” Zhang said — but not so well when glucose is the initial stock. In fact, attempts at direct glucose conversion created so many impurities that it was simpler to start with the fructose, less common in nature than glucose.

Zhang and his team, working with a high-throughput reactor capable of testing 96 metal halide catalysts at various temperatures, discovered that a particular metal — chromium chloride — was by far the most effective at converting glucose to HMF with few impurities and, as such reactions go, at low temperature, 100 degrees centigrade.

“This, in my view, is breakthrough science in the renewable energy arena,” said J.M. White, IIC director and Robert A. Welch chair in materials chemistry at the University of Texas. “This work opens the way for fundamental catalysis science in a novel solvent.”

The chemistry at work remains largely a mystery, Zhang said, but he suspects that metal chloride catalysts work during an atom-swapping phase that sugar molecules go through called mutarotation, in which an H (hydrogen) and OH (hydroxyl group) trade places.

The hydrogen-hydroxyl position-switch that allows the catalytic conversion was verified by nuclear magnetic resonance performed at the William R. Wiley Environmental Molecular Sciences Laboratory, a DOE national scientific user facility located at PNNL. During
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Source:DOE/Pacific Northwest National Laboratory


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