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

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2022-11-01
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Liu, Hengzhou
Patel, Deep M.
Chen, Yifu
Lee, Jungkuk
Lee, Ting-Han
Roling, Luke T.
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American Chemical Society
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Cady, Sarah
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Cochran, Eric
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Li, Wenzhen
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Chemistry

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Ames National Laboratory

Ames National Laboratory is a government-owned, contractor-operated national laboratory of the U.S. Department of Energy (DOE), operated by and located on the campus of Iowa State University in Ames, Iowa.

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Bioeconomy Institute
The Bioeconomy Institute at Iowa State University leads the nation and world in establishing the bioeconomy, where society obtains renewable fuel, energy, chemicals, and materials from agricultural sources. The institute seeks to advance the use of biorenewable resources for the production of fuels, energy, chemicals, and materials. The Institute will assure Iowa’s prominence in the revolution that is changing the way society obtains its essential sources of energy and carbon. This revolution will dramatically reduce our dependence on petroleum. Instead of fossil sources of carbon and energy, the bioeconomy will use biomass (including lignocellulose, starches, oils and proteins) as a renewable resource to sustain economic growth and prosperity. Agriculture will supply renewable energy and carbon to the bioeconomy while engineering will transform these resources into transportation fuels, commodity chemicals, and electric power. This transformation, however, must be done in a manner that meets our present needs without compromising those of future generations.
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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.
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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.
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