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Dopant-Directed Activity in NiOOH: Distinct Fe, Co, and Cu Roles in Electrocatalytic HMF Oxidation to FDCA
Sanphong Khamhom1,2, Natjanan Songserm1,2, Nuttapon Yodsin3
1Department of Chemistry, Faculty of Science, Kasetsart University, Bangkok, Thailand.
Chemsuschem
|April 25, 2026
Summary
Iron-doped nickel oxyhydroxide (NiFeOOH) electrocatalysts efficiently convert 5-hydroxymethylfurfural (HMF) to 2,5-furandicarboxylic acid (FDCA), a key bio-based plastic precursor. This study details how dopants like iron optimize catalyst performance for sustainable chemical production.
Area of Science:
- Electrochemistry
- Materials Science
- Sustainable Chemistry
Background:
- 5-hydroxymethylfurfural (HMF) oxidation to 2,5-furandicarboxylic acid (FDCA) is a crucial step towards bio-based plastics, offering an alternative to petroleum-derived polyethylene terephthalate (PET).
- Developing efficient and selective electrocatalysts is essential for the economic viability of this sustainable chemical transformation.
Purpose of the Study:
- To systematically compare the effects of Fe, Co, and Cu dopants on NiOOH electrocatalysts for HMF oxidation reaction (HMFOR) in alkaline media.
- To elucidate the specific roles of different dopants in tuning catalyst activity, selectivity, and reaction mechanisms.
Main Methods:
- Synthesis of NiOOH electrocatalysts doped with Fe, Co, and Cu using pulsed electrodeposition with controlled loadings and dopant distributions.
- Electrocatalytic performance evaluation including Faradaic efficiency (FE) for FDCA and HMF conversion.
- Mechanistic investigations using potential-dependent product analysis, in situ Raman spectroscopy, kinetic studies, and density functional theory (DFT) calculations.
Main Results:
- NiFeOOH exhibited the highest activity and selectivity, achieving 87.42% FEFDCA and 98.85% FEHMFOR at 1.53 V vs RHE.
- Scaled-up electrode performance demonstrated near-quantitative HMF conversion (99.98%) and high FDCA yield (95.45%) over 6 hours with excellent durability.
- DFT and experimental results revealed dopant-specific functions: Fe tunes electronic structure and adsorption, Co increases surface area, and Cu modifies the reaction pathway.
Conclusions:
- Fe doping in NiOOH is highly effective for enhancing HMFOR performance by optimizing electronic structure and substrate interaction.
- Different dopants provide distinct control over catalyst morphology and intrinsic reactivity, highlighting opportunities for tailored catalyst design.
- These findings support the development of advanced Ni-based electrocatalysts and motivate multidopant strategies for superior bio-based chemical production.
Keywords:
surface area effect2,5‐furandicarboxylic acid5‐hydroxymethylfurfural oxidationdopant effectselectrocatalysiselectronic structurenickel oxyhydroxideMore Related Videos
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