Woody bio-oil represents a promising renewable fuel for alkaline fuel cells (AFCs); however, its direct electrochemical utilization is fundamentally constrained by the low intrinsic electroactivity of crude bio-oil arising from its compositional complexity and limited abundance of redox-active species. In this work, a targeted solvent-extraction strategy is developed to selectively enrich electroactive components from woody bio-oil, thereby enabling the functional upgrading of biomass-derived liquids toward electrochemical energy conversion. Among the solvents evaluated, ethyl acetate exhibits a pronounced selectivity for alcohols, sugars, and phenolic compounds, establishing a quantitative correlation between bio-oil composition and AFC discharge performance. Under optimized extraction and operating conditions, the resulting AFC with 6 mL bio-oil as fuel achieves a maximum current output of 12.15 mA with a sustained discharge duration of 24.27 h. Comparative GC–MS analyses conducted before and after AFC operation confirm that alcohols, sugars, and phenolic derivatives constitute the dominant contributors to anodic electro-oxidation under alkaline conditions, providing mechanistic insight into bio-oil electrochemical conversion. Collectively, this study advances an integrated strategy combining selective component enrichment and electrochemical optimization, and demonstrates the potential of lignocellulosic bio-oil as a functional electrochemical energy carrier for high-value biomass valorization.
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