Activation of formyl CH and hydroxyl OH bonds in HMF by the CuO(1 1 1) and Co₃O₄(1 1 0) surfaces: A DFT study

다국어 초록 (Multilingual Abstract)

<P><B>Abstract</B></P> <P>The first principle calculations with on-site Coulomb repulsion U terms were carried out to investigate the 5-hydroxymethylfurfural (HMF) adsorption on the CuO(1 1 1) and Co<SUB>3</SUB>O<SUB>4</SUB>(1 1 0) surfaces, two widely used oxidation catalysts. The adsorption of HMF molecule is energetically favoured in both cases, and HMF is more inclined to bridge adsorption via hydroxyl and formyl groups binding with surface O and metal sites. Moreover, the adsorption energy relies on both the coordination type of surface lattice oxygen to which the H atom binds and the formation of H-bond involving hydroxyl and formyl groups on the adsorbed HMF. Also, the hydroxyl OH bond breaking is very easy and is likely to be the first step in HMF oxidation, and then the OH insertion reaction to produce 2,5-furandicarboxylic acid (FDCA). The corresponding experimental results also show that the CuO and Co<SUB>3</SUB>O<SUB>4</SUB> surfaces are promising candidate catalysts.</P> <P><B>Highlights</B></P> <P> <UL> <LI> CuO(1 1 1) and Co<SUB>3</SUB>O<SUB>4</SUB>(1 1 0) surfaces catalyze the oxidation of 5-hydroxymethylfurfural (HMF). </LI> <LI> Initial binding was formed through bridged-adsorption with O atoms in HMF. </LI> <LI> Oxidation reaction proceeds through the OH bond breaking pathway. </LI> </UL> </P> <P><B>Graphical abstract</B></P> <P>Schematic potential energy diagram for the formyl CH and hydroxyl OH bonds of HMF dissociation on CuO(1 1 1) and Co<SUB>3</SUB>O<SUB>4</SUB>(1 1 0) surfaces. Obviously, the hydroxyl OH bond breaking is easier than that of the formyl CH bond on the two surfaces, which indicates the first step of oxidation of HMF to FDCA should be hydroxyl OH bond breaking.</P> <P>[DISPLAY OMISSION]</P>