MoO x-Decorated Co-Based Catalysts toward the Hydrodeoxygenation Reaction of Biomass-Derived Platform Molecules

ACS Appl Mater Interfaces. 2021 Jul 14;13(27):31799-31807. doi: 10.1021/acsami.1c10599. Epub 2021 Jul 1.

Abstract

Catalytic conversion of a biomass derivative (levulinic acid, LA) to a high value-added product (γ-valerolactone, GVL) has attracted much attention, in which the control of catalytic selectivity plays an important role. Herein, a stepwise method was developed to prepare Co-MoOx catalysts via topological transformation (calcination reduction) from layered double hydroxide (Mo/CoAl-LDH) precursors. X-ray diffraction, high-resolution transmission electron microscopy, and hydrogen temperature-programmed reduction demonstrate the formation of MoOx-decorated Co structures of Co-MoOx samples. Remarkably, the sample that is reduced at 500 °C is featured with the most abundant interfacial Coδ+ (denoted as Co-MoOx-500), which exhibits an excellent catalytic performance toward the hydrodeoxygenation (HDO) reaction of several biomass-derived platform molecules (furfural, FAL; succinic acid, SA; 5-hydroxymethyl-furfural, HMF; and levulinic acid, LA). Especially, this optimal catalyst displays a high yield (99%) toward the HDO reaction of LA to GVL, which stands at the highest level among non-noble metal catalysts. The combination of in situ FT-IR characterization and theoretical calculation further confirms that interfacial Coδ+ sites in Co-MoOx-500 act as adsorption active sites for the polarization of a C═O bond in an LA molecule, which simultaneously promotes C═O hydrogenation and C-O cleavage. Moreover, the MoOx overlayer suppresses the formation of byproducts by covering the Co0 sites. This work offers a cost-effective and efficient catalyst, which can be potentially applied in catalytic conversion of biomass-derived platform molecules.

Keywords: MoOx-decorated Co-based catalysts; hydrodeoxygenation reaction; layered double hydroxides; levulinic acid; structure−selectivity correlation.

MeSH terms

  • Biomass*
  • Catalysis
  • Cobalt / chemistry*
  • Hydrogenation
  • Levulinic Acids / chemistry*
  • Temperature
  • Tilidine / chemistry*

Substances

  • Levulinic Acids
  • Cobalt
  • Tilidine
  • levulinic acid