Ultra-low temperature direct reconstruction of biomass fermentation of ethanol to higher alcohols in water over thermostable hcp-Ni

Direct reconstruction of fermentation of ethanol in water with high water content to higher alcohols is a promising way to produce value-added fine chemicals and bio-fuels. In particular, aqueous ethanol reconstruction under near-ambient conditions is a milestone goal, but facing great challenges. Herein, the highly active and thermostable hexagonal-close-packed (hcp) Ni dominated hcp/fcc-Ni@C catalyst was fabricated via a facile surfactant-induced carbonization strategy for direct reconstruction of fermentation of ethanol solution to C4+ higher alcohols at near-ambient temperature (<100 °C). A superior performance of >99% higher alcohol selectivity with 17.6% ethanol conversion was achieved. DFT analysis revealed a low energy barrier of ethanol dehydrogenation (rate-determining step) over hcp-Ni, which is crucial for the ultra-low temperature ethanol reconstruction in water. The induction effect of the amide group in surfactant precursors is the key to the formation of hcp-Ni. This work provides new insight into producing bio-based higher alcohols from readily accessible aqueous fermentation of ethanol under mild reaction conditions, which is very promising for large-scale combined applications in industry.