Copper-zinc alloy nanopowder: a robust precious-metal-free catalyst for the conversion of 5-hydroxymethylfurfural.

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Abstract

Noble-metal-free copper-zinc nanoalloy (<150 nm) is found to be uniquely suited for the highly selective catalytic conversion of 5-hydroxymethylfurfural (HMF) to potential biofuels or chemical building blocks. Clean mixtures of 2,5-dimethylfuran (DMF) and 2,5-dimethyltetrahydrofuran (DMTHF) with combined product yields up to 97 % were obtained at 200-220 °C using 20-30 bar H2 . It is also possible to convert 10 wt % HMF solutions in CPME, with an excellent DMF yield of 90 %. Milder temperatures favor selective (95 %) formation of 2,5-furandimethanol (FDM). The one-pot conversion of fructose to valuable furan-ethers was also explored. Recycling experiments for DMF production show remarkable catalyst stability. Transmission electron microscopy (TEM) characterization provides more insight into morphological changes of this intriguing class of materials during catalysis.

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Technology development for the production of biobased products from biorefinery carbohydrates—the US Department of Energy’s “Top 10” revisited

Joseph J Bozell, Gene R. Petersen (2010)

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Hydroxymethylfurfural, a versatile platform chemical made from renewable resources.

Robert-Jan van Putten, Jan C. van der Waal, Ed de Jong … (2013)

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Simple chemical transformation of lignocellulosic biomass into furans for fuels and chemicals.

Joseph Binder, Ronald T. Raines (2009)

Lignocellulosic biomass is a plentiful and renewable resource for fuels and chemicals. Despite this potential, nearly all renewable fuels and chemicals are now produced from edible resources, such as starch, sugars, and oils; the challenges imposed by notoriously recalcitrant and heterogeneous lignocellulosic feedstocks have made their production from nonfood biomass inefficient and uneconomical. Here, we report that N,N-dimethylacetamide (DMA) containing lithium chloride (LiCl) is a privileged solvent that enables the synthesis of the renewable platform chemical 5-hydroxymethylfurfural (HMF) in a single step and unprecedented yield from untreated lignocellulosic biomass, as well as from purified cellulose, glucose, and fructose. The conversion of cellulose into HMF is unabated by the presence of other biomass components, such as lignin and protein. Mechanistic analyses reveal that loosely ion-paired halide ions in DMA-LiCl are critical for the remarkable rapidity (1-5 h) and yield (up to 92%) of this low-temperature (