Electrocatalysis poses many potential advantages for distributed scale biomass valorization. Furanic biomass derivatives such as furfural and 5-hydroxymethylfurfural (HMF) can provide access to a number of value-added chemicals by partial oxidation, including furoic acid, maleic acid, and 2,5-furandicarboxylic acid (FDCA). Here, we have utilized differential reactor studies with online electrochemical mass spectrometry (OLEMS), as well as in situ attenuated total reflectance-surface-enhanced infrared reflection-absorption spectroscopy (ATR-SEIRAS), to probe these reaction pathways on various metal electrodes. Experimental insights are combined with computational results to piece together plausible mechanisms. In particular we find tradeoffs between decarbonylation activity on Pt-group electrodes and and self-assembly of furoate intermediates on noble metals to be critical selectivity and rate determining steps.  Strategies for improved catalyst design will be discussed.

Electro-oxidation pathways for biomass-derived ufrans

ACS Spring 2022

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