Mechanistic Study of Selective Electrochemical Reduction of Hydroxymethyl Furfural using Grand-Canonical DFT
Résumé
Among biomass-platform molecules, 5-hydroxymethylfurfural
(HMF) plays an important role since its great potential in the production of
industrial monomers, fuels, and pesticides. One of its most interesting
products is 2,5-bishydroxymethylfuran (BHMF), that can be used in relevant
industrial polymerization processes, such as for polyethers, polyesters and
polyamides. In this context, the electrochemical reduction of HMF to BHMF is
gaining an increasing interest. The main challenge is to achieve a high
faradic efficiency and a good selectivity. Experimentally, it has been shown
that using AgCu bimetallic electrocatalysts allowed to achieve a higher
conversion, higher selectivity and higher faradic efficiency than the
monometallic counter-part.
Still, a better understanding of the reaction network is necessary to limit even
further the generation of secondary products, in particular humins and to limit
the overpotential. Using grand canonical periodic DFT, we investigated the
conversion of HMF into BHMF but also the possible side routes such as the
ones yielding to methyl furfural and methyl furfuryl alcohol which involves a
C-O scission but also the C-C coupling yielding hydrofuroin, a precusor of
humins. This extended reaction network has been explored on Cu, Ag and
alloy models surfaces. The competition with the hydrogen evolution reaction
was also addressed by considering the H coverage in function of the pH and
the potential. The influence of the polarization of the electrode is taken into
account on the C-C and C-O barrier using a grand canonical approach, which
has been shown to be important in cases where the surface dipole induced
by the adsorbate is changing during the reaction