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Efficient radical-driving electrocatalytic dimerization of furfural to jet fuel precursors using WMoB nanoflakes

Xiaodie Zhang,Bin Liu,Yuchen Wang,Ying Long,Zhenhao Xu,Hua-Tay Lin,Rafael Luque,Kai Yan

Electrocatalytic dimerization (ECD) of biomass platform molecules represents a promising route for sustainable fuel and chemical production. However, the widespread application of ECD is limited by catalysts with low activity, undesired product selectivity and poor durability. Herein, we demonstrate the development of high-performing and stable transition metal borides WMoB nanoflakes catalyst for the ECD of biomass-derived furfural (FF) into hydrofuroin (HFN) which is a precursor of jet fuel. As-obtained WMoB nanoflake-likes electrocatalyst, prepared by solvent-free mechanical alloying strategy, could achieve FF conversion of 80.5% and an HFN selectivity of 76.7% at −0.59 V vs. RHE (Reversible Hydrogen Electrode), which is 3.7 times more selective than WB for HFN (20.4%). Experimental and theoretical studies, including X-ray absorption fine structure (XAFS), electrochemical analysis, in situ electron paramagnetic resonance (EPR), kinetic isotope effect (KIE) evaluation and density functional theory (DFT) calculations reveal that high coverage of furan radicals on WMoB nanoflakes play a crucial role for the ECD reaction. The furan radicals-driven C–C coupling reaction offers an alternative strategy to synthesize valuable products from biomass refineries.