Role of Surface Cooperative Effect in Copper Catalysts toward Highly Selective Synthesis of Valeric Biofuels
2017
Li, Wei | Li, Yizhen | Fan, Guoli | Yang, Lan | Li, Feng
Currently, the catalytic conversion of biomass-derived compounds into biofuels is of great significance in terms of environmental protection and sustainable development. Among them, valeric esters derived from γ-valerolactone (GVL) are regarded as one of the most promising alternatives to fossil fuels. Herein, the highly efficient one-pot transformation of GVL to produce a series of valeric esters was successfully achieved over novel ZrO₂-incorporated ZnAl₂O₄-composite-supported Cu-based catalysts. An extensive investigation gave clear evidence that the incorporation of ZrO₂ into composites could lead to the enhanced metal dispersion and surface acidity. Especially, the catalyst with a Zr/Zn mass ratio of 0.2 exhibited the best selectivity of 99% in the transformation of GVL into pentyl valerate to date, together with a comparable conversion of 91% with respect to the Cu-based catalyst previously reported. The superior catalytic performance was attributable to the surface cooperation effect between highly dispersed active copper species and abundant surface acid sites. Especially, different surface types of acidic sites on catalysts could induce the reaction to efficiently proceed in different paths. The present work provides a valuable approach for precious metal substitution research in future large-scale biorefineries.
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