What Drives the Selectivity of 5-(Hydroxymethyl)furfural Electroreduction over Copper in Mildly Basic Medium?
Abstract
2,5-Bishydroxymethylfuran (BHMF) is an important bio-based monomer that can be produced via the electrochemical reduction of 5-(hydroxymethyl)furfural (HMF) on Cu electrocatalysts. Under mildly alkaline conditions, however, BHMF formation competes with hydrodimerization to 5,5′-bis(hydroxymethyl)hydrofuroin (BHH) and oligomerization, particularly at HMF concentrations relevant for scale-up. Here, we combine electrochemical experiments and grand-canonical density functional theory (GC-DFT) to elucidate the origin of these competing pathways during HMF electroreduction on Cu-based foam catalysts at pH 9.2. Our results suggest that BHH formation and oligomerization arise from two distinct mechanisms: hydrodimerization might proceed via surface-catalyzed C–C coupling between adsorbed HMF species, whereas oligomerization is associated with the desorption of a ketyl intermediate into the electrochemical double layer. In contrast, BHMF formation preferentially occurs through the hydrogenation of an alkoxyl intermediate. The relative contribution of these pathways is modulated by catalyst morphology and the electroactive Cu surface area. Increasing the surface area through Cu nanoparticle electrodeposition enhances BHMF selectivity from 40% to 58% at 50 mM HMF and significantly suppresses oligomerization at –0.51 V vs RHE. Overall, our results highlight the importance of balancing HMF surface availability and H* availability and provide a mechanistic framework linking catalyst morphology and electrochemical conditions to control the selective HMF electroreduction on Cu and offer design principles for maximizing BHMF yields while minimizing hydrodimerization and carbon loss.
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BibTeX
@article{loprete2026what,
title = {{What Drives the Selectivity of 5-(Hydroxymethyl)furfural Electroreduction over Copper in Mildly Basic Medium?}},
author = {Fabio Loprete and Giovanni Malagoli and Adriano Sacco and Riccardo Tarroni and Stephan N. Steinmann and Ivan Rivalta and Carine Michel and Patricia Benito},
journal = {ACS Catalysis},
year = {2026},
month = sep,
doi = {10.1021/acscatal.6c05142},
url = {https://hal.science/hal-05775078v1},
note = {CC BY-NC 4.0},
}
RIS
TY - JOUR
TI - What Drives the Selectivity of 5-(Hydroxymethyl)furfural Electroreduction over Copper in Mildly Basic Medium?
AU - Fabio Loprete
AU - Giovanni Malagoli
AU - Adriano Sacco
AU - Riccardo Tarroni
AU - Stephan N. Steinmann
AU - Ivan Rivalta
AU - Carine Michel
AU - Patricia Benito
PY - 2026
DA - 2026/09/26
JO - ACS Catalysis
DO - 10.1021/acscatal.6c05142
UR - https://hal.science/hal-05775078v1
AB - 2,5-Bishydroxymethylfuran (BHMF) is an important bio-based monomer that can be produced via the electrochemical reduction of 5-(hydroxymethyl)furfural (HMF) on Cu electrocatalysts. Under mildly alkaline conditions, however, BHMF formation competes with hydrodimerization to 5,5′-bis(hydroxymethyl)hydrofuroin (BHH) and oligomerization, particularly at HMF concentrations relevant for scale-up. Here, we combine electrochemical experiments and grand-canonical density functional theory (GC-DFT) to elucidate the origin of these competing pathways during HMF electroreduction on Cu-based foam catalysts at pH 9.2. Our results suggest that BHH formation and oligomerization arise from two distinct mechanisms: hydrodimerization might proceed via surface-catalyzed C–C coupling between adsorbed HMF species, whereas oligomerization is associated with the desorption of a ketyl intermediate into the electrochemical double layer. In contrast, BHMF formation preferentially occurs through the hydrogenation of an alkoxyl intermediate. The relative contribution of these pathways is modulated by catalyst morphology and the electroactive Cu surface area. Increasing the surface area through Cu nanoparticle electrodeposition enhances BHMF selectivity from 40% to 58% at 50 mM HMF and significantly suppresses oligomerization at –0.51 V vs RHE. Overall, our results highlight the importance of balancing HMF surface availability and H* availability and provide a mechanistic framework linking catalyst morphology and electrochemical conditions to control the selective HMF electroreduction on Cu and offer design principles for maximizing BHMF yields while minimizing hydrodimerization and carbon loss.
SN - 2155-5435
SN - 2155-5435
ER -