Electro-oxidation of furfural on gold is limited by furoate self-assembly

Alex M. Román; Naveen Agrawal; Joseph C. Hasse; Michael J. Janik; J. Will Medlin; Adam Holewinski

doi:10.1016/j.jcat.2020.08.034

Electro-oxidation of furfural on gold is limited by furoate self-assembly

Alex M. Román, Naveen Agrawal, Joseph C. Hasse, Michael J. Janik, J. Will Medlin, Adam Holewinski

Research output: Contribution to journal › Article › peer-review

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Abstract

Processing of biomass-derived compounds with electrocatalysis has shown promise to directly couple the production of valuable feedstocks with the storage of renewably produced electricity. One potential route of electrocatalytic conversion is the partial oxidation of furfural to furoic acid (FA), a precursor to 2,5-furandicarboxylic acid (FDCA). We have utilized differential electrochemical reactor studies along with infrared spectroscopy (ATR-SEIRAS) experiments and density functional theory (DFT) calculations to probe the oxidative reaction pathways of furfural on gold catalysts in acidic electrolyte. We find furfural electro-oxidation activity (~2 µA/cm²_Au at 1.0 V_RHE) to be an order of magnitude higher than that observed on Pt/C. 96 ± 6% Faradaic efficiency to FA is achieved at 0.8 V_RHE. Product desorption is rate limiting, and spectroscopic evidence indicates that the most abundant intermediate is surface furoate. Deeper oxidation products observed with dilution of furfural suggest that self-assembly of the furoate species contributes to selectivity.

Original language	English (US)
Pages (from-to)	327-335
Number of pages	9
Journal	Journal of Catalysis
Volume	391
DOIs	https://doi.org/10.1016/j.jcat.2020.08.034
State	Published - Nov 2020

All Science Journal Classification (ASJC) codes

Catalysis
Physical and Theoretical Chemistry

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10.1016/j.jcat.2020.08.034

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title = "Electro-oxidation of furfural on gold is limited by furoate self-assembly",

abstract = "Processing of biomass-derived compounds with electrocatalysis has shown promise to directly couple the production of valuable feedstocks with the storage of renewably produced electricity. One potential route of electrocatalytic conversion is the partial oxidation of furfural to furoic acid (FA), a precursor to 2,5-furandicarboxylic acid (FDCA). We have utilized differential electrochemical reactor studies along with infrared spectroscopy (ATR-SEIRAS) experiments and density functional theory (DFT) calculations to probe the oxidative reaction pathways of furfural on gold catalysts in acidic electrolyte. We find furfural electro-oxidation activity (~2 µA/cm2Au at 1.0 VRHE) to be an order of magnitude higher than that observed on Pt/C. 96 ± 6% Faradaic efficiency to FA is achieved at 0.8 VRHE. Product desorption is rate limiting, and spectroscopic evidence indicates that the most abundant intermediate is surface furoate. Deeper oxidation products observed with dilution of furfural suggest that self-assembly of the furoate species contributes to selectivity.",

author = "Rom{\'a}n, {Alex M.} and Naveen Agrawal and Hasse, {Joseph C.} and Janik, {Michael J.} and Medlin, {J. Will} and Adam Holewinski",

note = "Publisher Copyright: {\textcopyright} 2020 Elsevier Inc.",

year = "2020",

month = nov,

doi = "10.1016/j.jcat.2020.08.034",

language = "English (US)",

volume = "391",

pages = "327--335",

journal = "Journal of Catalysis",

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publisher = "Academic Press Inc.",

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T1 - Electro-oxidation of furfural on gold is limited by furoate self-assembly

AU - Román, Alex M.

AU - Agrawal, Naveen

AU - Hasse, Joseph C.

AU - Janik, Michael J.

AU - Medlin, J. Will

AU - Holewinski, Adam

PY - 2020/11

Y1 - 2020/11

N2 - Processing of biomass-derived compounds with electrocatalysis has shown promise to directly couple the production of valuable feedstocks with the storage of renewably produced electricity. One potential route of electrocatalytic conversion is the partial oxidation of furfural to furoic acid (FA), a precursor to 2,5-furandicarboxylic acid (FDCA). We have utilized differential electrochemical reactor studies along with infrared spectroscopy (ATR-SEIRAS) experiments and density functional theory (DFT) calculations to probe the oxidative reaction pathways of furfural on gold catalysts in acidic electrolyte. We find furfural electro-oxidation activity (~2 µA/cm2Au at 1.0 VRHE) to be an order of magnitude higher than that observed on Pt/C. 96 ± 6% Faradaic efficiency to FA is achieved at 0.8 VRHE. Product desorption is rate limiting, and spectroscopic evidence indicates that the most abundant intermediate is surface furoate. Deeper oxidation products observed with dilution of furfural suggest that self-assembly of the furoate species contributes to selectivity.

AB - Processing of biomass-derived compounds with electrocatalysis has shown promise to directly couple the production of valuable feedstocks with the storage of renewably produced electricity. One potential route of electrocatalytic conversion is the partial oxidation of furfural to furoic acid (FA), a precursor to 2,5-furandicarboxylic acid (FDCA). We have utilized differential electrochemical reactor studies along with infrared spectroscopy (ATR-SEIRAS) experiments and density functional theory (DFT) calculations to probe the oxidative reaction pathways of furfural on gold catalysts in acidic electrolyte. We find furfural electro-oxidation activity (~2 µA/cm2Au at 1.0 VRHE) to be an order of magnitude higher than that observed on Pt/C. 96 ± 6% Faradaic efficiency to FA is achieved at 0.8 VRHE. Product desorption is rate limiting, and spectroscopic evidence indicates that the most abundant intermediate is surface furoate. Deeper oxidation products observed with dilution of furfural suggest that self-assembly of the furoate species contributes to selectivity.

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SN - 0021-9517

VL - 391

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EP - 335

JO - Journal of Catalysis

JF - Journal of Catalysis

ER -

Electro-oxidation of furfural on gold is limited by furoate self-assembly

Abstract

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