Sustainable biofuel production via one-pot C-C coupling and hydrodeoxygenation of biobased compound over versatile LaNi1-xCuxO3±δ inorganic perovskites

Processing of biomass to energy chemicals starts from pyrolysis to oxygenated platform molecules that require hydrodeoxygenation (HDO) to biofuels. Also, the composition and carbon chain lengths from direct pyrolysis make direct utilization in specialized engines difficult due to compatibility issues. Therefore, tailormade carbon-carbon (C-C) coupling and hydrodeoxygenation of bioderived platform molecules become central to attainment of green and sustainable biofuels. In this work, the catalytic activity of LaNi 1-x Cu x O 3±δ (0 ≤ x ≤ 1) perovskites was assessed in the attainment of biofuels, including biogasoline, biokerosene, and biodiesel. The acquired results suggest that the metal ratios of the B-site cations (B and B ` ) significantly influence the catalytic performance of the perovskites in the conversion of biobased compound to biofuels. Notably, the synthesized LaNi 0.5 Cu 0.5 O 3±δ perovskites demonstrated efficient one pot C-C coupling and HDO of methyl benzoate and dodecylmagnesium bromide, a Grignard reagent, achieving 58.1% conversion and 100% selectivity towards fuel hydrocarbons at relatively low temperatures. While reactions involving a Grignard reagent normally yield oxygenated products, for the first time the as-synthesized catalysts demonstrated a highly efficient one-pot C-C coupling and dehydration of the biofuel intermediates. Thus, this study provides valuable insights into the design of effective perovskite catalysts for sustainable synthesis of biofuels by looking at the effect of different alcohols as reaction media. Furthermore, this work presents the first use of a Grignard reagent for chain length extension in sustainable synthesis of biofuels. • One-pot C-C coupling and hydrodeoxygenation over perovskite catalysts is a sustainable option for biofuel synthesis. • Biofuels’ components can be altered by tunning the B-site of catalytically active perovskite oxides. • The reaction medium controls the product selectivity of biofuel components. • The nature of the catalyst dictates adsorption sites and aids in the design of metal oxide catalysts.