Sequentially Coupled Oxidative Coupling-Hydrodeoxygenation for Aliphatic Hydrocarbons Production from Furfural

The transformation of lignocellulosic biomass into long-chain aliphatic hydrocarbons (C7–C9) represents a pivotal route for fuel/additive production, yet conventional processes often suffer from low carbon efficiency due to uncontrolled C–C cleavage. Herein, we report an innovative sequentially coupled coupling–hydrodeoxygenation strategy that enables the complete conversion of furfural and short-chain alcohols (C2–C4) into corresponding aliphatic hydrocarbons with 100% carbon atom economy. A triple single-atom catalyst (Co/Cu/Ni–TSA), featuring atomically dispersed Co, Cu, and Ni sites on a hierarchical N-doped carbon framework, was designed to catalyze both the oxidative coupling and subsequent hydrodeoxygenation steps in a continuous flow system. Mechanistic studies unveil synergistic interactions among the metal single atoms, wherein Co and Cu facilitate substrate activation and coupling, while Ni modulates electronic structures to lower energy barriers. The integrated process demonstrates good stability and scalability, converting 32.4 g of furfural with isopropanol into 39.1 g of n-octane at 99% selectivity over 216 h of continuous operation. This work establishes a paradigm for efficient and atom-economical biomass upgrading to drop-in hydrocarbon fuels.