Biomass-derived feedstocks are sustainable alternatives to petroleum-based feedstocks for the production of fuels and value-added chemicals such as precursors for bioplastics. Research on biomass alcohol electrooxidation has yielded significant knowledge on the mechanisms of the rate-determining steps, including transition metal redox mediated and potential-dependent pathways. However, additional design principles are needed as the reported kinetic overpotentials are still prohibitively large for efficient electrosynthesis. Here, we use experiment and theory to investigate how transition metal oxyhydroxide catalysts and their microenvironments work in concert to steer biomass alcohol electrooxidation activity. First, I will discuss how Fe incorporation into Ni(OH) 2 impacts the phase transition to NiOOH, and thus, the onset potential of benzyl alcohol electrooxidation through the redox mediated mechanism. Next, I will highlight the role of the catalyst microenvironment, and particularly the electrolyte pH, in controlling chemical reactions with substrate molecules such as hydroxymethylfurfural to form reactive intermediates such as alkoxides and geminal diols for electrooxidation on NiOOH. Finally, I will discuss how hydride transfer reaction energies can be used as an activity descriptor for the design of more active catalysts for biomass alcohol electrooxidation.

Insights on steering reaction networks for biomass alcohol electrooxidation through active site and microenvironment effects

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