AbstractCatalytic conversion of biomass‐derived 5‐(hydroxymethyl)furfural (5‐HMF) into carbon‐increased hydrocarbons as drop‐in energy‐rich biofuels has received a great deal of concern for the development of sustainable chemical industry. Here, we demonstrate a one‐pot conversion of 5‐HMF into C9‐alkanes on one single catalyst, acidic–basic layered double oxides (Mg(Al)(Zr)O) supported CuCo alloy. The well‐defined multifunctional catalytic sites with harmonious combination carry out cascade catalysis, affording C9‐alkanes (including 30% of more value‐added branched‐cycloalkanes) in 83% yield. The basic–acidic sites on Mg(Al)(Zr)O show high activity for aldol condensation of 5‐HMF and acetone, producing 4‐[5‐(hydroxymethyl)‐2‐furanyl]‐3‐buten‐2‐one (HAc) in a yield of >99%. The engineered Co–Cu–Co linkages on supported CuCo perform efficient hydrodeoxygenation, affording C9‐alkanes in a selectivity of 96% from HAc. C9‐cycloalkanes are generated from the cyclization of the corresponding monohydric alcohol intermediates by the synergy of acidic and CuCo sites in the hydrodeoxygenation reaction.
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