Unraveling Electroreductive Mechanisms of Biomass-Derived Aldehydes via Tailoring Interfacial Environments

dc.contributor.author Liu, Hengzhou
dc.contributor.author Patel, Deep M.
dc.contributor.author Chen, Yifu
dc.contributor.author Lee, Jungkuk
dc.contributor.author Lee, Ting-Han
dc.contributor.author Cady, Sarah
dc.contributor.author Cochran, Eric
dc.contributor.author Roling, Luke T.
dc.contributor.author Li, Wenzhen
dc.contributor.department Chemistry
dc.contributor.department Chemical and Biological Engineering
dc.contributor.department Ames National Laboratory
dc.contributor.department Bioeconomy Institute
dc.date.accessioned 2022-11-07T19:44:36Z
dc.date.available 2022-11-07T19:44:36Z
dc.date.issued 2022-11-01
dc.description.abstract Electrochemical reduction of biomass-derived feedstocks holds great promise to produce value-added chemicals or fuels driven by renewable electricity. However, mechanistic understanding of the aldehyde reduction toward valuable products at the molecular level within the interfacial regions is still lacking. Herein, through tailoring the local environments, including H/D composition and local H3O+ and H2O content, we studied the furfural reduction on Pb electrodes under acid conditions and elucidated the pathways toward three key products: furfuryl alcohol (FA), 2-methylfuran (MF), and hydrofuroin. By combining isotopic labeling and incorporation studies, we revealed that the source of protons (H2O and H3O+) plays a critical role in the hydrogenation and hydrogenolysis pathways toward FA and MF, respectively. In particular, the product-selective kinetic isotopic effect of H/D and the surface-property-dependent hydrogenation/deuteration pathway strongly impacted the generation of FA but not MF, owing to their different rate-determining steps. Electrokinetic studies further suggested Langmuir–Hinshelwood and Eley–Rideal pathways in the formation of FA and MF, respectively. Through modifying the double layer by cations with large radii, we further correlated the product selectivity (FA and MF) with interfacial environments (local H3O+ and H2O contents, interfacial electric field, and differential capacitances). Finally, experimental and computational investigations suggested competitive pathways toward hydrofuroin and FA: hydrofuroin is favorably produced in the electrolyte through the self-coupling of ketyl radicals, which are formed from outer-sphere, single-electron transfer, while FA is generated from hydrogenation of the adsorbed furfural/ketyl radical on the electrode surface.
dc.description.comments This document is the unedited Author’s version of a Submitted Work that was subsequently accepted for publication in ACS Catalysis, copyright © 2022 American Chemical Society after peer review. To access the final edited and published work see DOI: 10.1021/acscatal.2c03163. Posted with permission.
dc.identifier.uri https://dr.lib.iastate.edu/handle/20.500.12876/EwpaEyGv
dc.language.iso en
dc.publisher American Chemical Society
dc.source.uri https://doi.org/10.1021/acscatal.2c03163 *
dc.subject.disciplines DegreeDisciplines::Engineering::Chemical Engineering::Catalysis and Reaction Engineering
dc.subject.disciplines DegreeDisciplines::Physical Sciences and Mathematics::Environmental Sciences::Oil, Gas, and Energy
dc.subject.keywords biomass-derived aldehyde
dc.subject.keywords electrocatalytic hydrogenation
dc.subject.keywords pathway
dc.subject.keywords selectivity
dc.subject.keywords outer-sphere
dc.subject.keywords interfacial environments
dc.title Unraveling Electroreductive Mechanisms of Biomass-Derived Aldehydes via Tailoring Interfacial Environments
dc.type Article
dspace.entity.type Publication
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