Spectral-architectural tuning of Au–Pd nanocatalysts for on-demand photocatalytic HMF oxidation
Abstract
The selective oxidation of biomass-derived 5-hydroxymethylfurfural (HMF) into highvalue intermediates and 2,5-furandicarboxylic acid (FDCA) is a key process in sustainable polymer manufacturing. However, conventional thermal processes often require harsh conditions that promote non-selective degradation or high-energy demand. Herein, we establish a comprehensive structure-light-reactivity relationship for the photo-assisted oxidation of HMF in water by systematically comparing zirconia-supported Au-Pd alloy and core-shell nanoarchitectures under thermal and photocatalytic conditions. Monochromatic irradiation at 365, 450, and 523 nm was employed to decouple the contributions of UV photolysis, visible-light activation, and localized surface plasmon resonance (LSPR) of gold. We identify the surface Pd density as the primary structural descriptor governing oxidation depth, while the nanoarchitecture dictates the light-harvesting mechanism. Under thermal conditions, the alloy configuration dominates through synergistic electronic and geometric ensemble effects. Intriguingly, this catalytic ranking undergoes a fundamental reversal under 450 nm irradiation, with the Pd-rich core-shell architecture (AuPd500@ZrO2) outperforming the alloy and achieving near-complete HMF conversion (99.1%), together with significant selectivity toward FDCA (24.9%) and FFCA (25.9%). At 523 nm, close to the Au LSPR maximum, the ranking reverses again in favor of the alloy configuration. This double reversal demonstrated a wavelength-gated reaction steering mechanism where, for a fixed Au-Pd composition, nanoarchitecture alone determines the activity and selectivity. Crucially, the wavelength-dependent response enables precise, external control over product distributions without altering the baseline reaction parameters. Operating in an aqueous medium under mild conditions with low precious-metal loadings, this work demonstrates that combining rational nanostructure design with targeted spectral inputs offers a powerful tool for overcoming conventional thermal Sabatier limitations in renewable carbon upgrading.
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BibTeX
@article{pieretti2026spectralarchitectural,
title = {{Spectral-architectural tuning of Au–Pd nanocatalysts for on-demand photocatalytic HMF oxidation}},
author = {Filippo Pieretti and Leonardo Agnolon and Arthur Reymond and Ibrahim Abdelsalam and Almudena Marti and Nikolaos Dimitratos and Pedro H.C. Camargo and Robert Wojcieszak},
journal = {Materials Today Communications},
year = {2026},
month = oct,
doi = {10.1016/j.mtcomm.2026.116309},
url = {https://hal.science/hal-05779576v1},
note = {CC BY 4.0},
}
RIS
TY - JOUR
TI - Spectral-architectural tuning of Au–Pd nanocatalysts for on-demand photocatalytic HMF oxidation
AU - Filippo Pieretti
AU - Leonardo Agnolon
AU - Arthur Reymond
AU - Ibrahim Abdelsalam
AU - Almudena Marti
AU - Nikolaos Dimitratos
AU - Pedro H.C. Camargo
AU - Robert Wojcieszak
PY - 2026
DA - 2026/10/05
JO - Materials Today Communications
DO - 10.1016/j.mtcomm.2026.116309
UR - https://hal.science/hal-05779576v1
AB - The selective oxidation of biomass-derived 5-hydroxymethylfurfural (HMF) into highvalue intermediates and 2,5-furandicarboxylic acid (FDCA) is a key process in sustainable polymer manufacturing. However, conventional thermal processes often require harsh conditions that promote non-selective degradation or high-energy demand. Herein, we establish a comprehensive structure-light-reactivity relationship for the photo-assisted oxidation of HMF in water by systematically comparing zirconia-supported Au-Pd alloy and core-shell nanoarchitectures under thermal and photocatalytic conditions. Monochromatic irradiation at 365, 450, and 523 nm was employed to decouple the contributions of UV photolysis, visible-light activation, and localized surface plasmon resonance (LSPR) of gold. We identify the surface Pd density as the primary structural descriptor governing oxidation depth, while the nanoarchitecture dictates the light-harvesting mechanism. Under thermal conditions, the alloy configuration dominates through synergistic electronic and geometric ensemble effects. Intriguingly, this catalytic ranking undergoes a fundamental reversal under 450 nm irradiation, with the Pd-rich core-shell architecture (AuPd500@ZrO2) outperforming the alloy and achieving near-complete HMF conversion (99.1%), together with significant selectivity toward FDCA (24.9%) and FFCA (25.9%). At 523 nm, close to the Au LSPR maximum, the ranking reverses again in favor of the alloy configuration. This double reversal demonstrated a wavelength-gated reaction steering mechanism where, for a fixed Au-Pd composition, nanoarchitecture alone determines the activity and selectivity. Crucially, the wavelength-dependent response enables precise, external control over product distributions without altering the baseline reaction parameters. Operating in an aqueous medium under mild conditions with low precious-metal loadings, this work demonstrates that combining rational nanostructure design with targeted spectral inputs offers a powerful tool for overcoming conventional thermal Sabatier limitations in renewable carbon upgrading.
SN - 2352-4928
ER -