Demystifying furfural electrooxidation descriptors via laser-patterned dianionic sulfur-selenide fused metal-chalcogenides

Abstract

Utilizing electrocatalysis on biomass-derived furfural molecules affords a method for producing valuable feedstocks, offering a robust substitute to the traditionally sluggish oxygen evolution reaction (OER). This study introduces a pulsed laser ablation in liquids (PLAL) approach for synthesizing dianionic sulfur-selenide fused nickel-chalcogenides (Ni3SxSe4−x), facilitating electrochemical OER and furfural oxidation reaction (FOR) in alkaline solution. SeCl4 dissolves into Se2− and serves as an anionic source via PLAL without requiring a reducing agent. Incorporating Se and S anions into Ni3SxSe4−x modulates the electronic structure of Ni, thereby enhancing its intrinsic catalytic action and stability for OER. Furthermore, FOR catalyzed over Ni3SxSe4−x produces approximately 13.7 mM furoic acid with a selectivity of ∼73.14%, carbon balance of ∼89.94%, and a notable Faradaic efficiency of approximately 98.82% over 2 h at 1.58 V vs. RHE. In situ electrochemical–Raman probe identified the formation of NiOOH reactive species through surface restructuring under oxidation potential, acting as a terminal for both water and furfural molecules. This research underscores the effectiveness of laser-patterned nickel sulfo-selenide in modulating oxidation activity, significantly contributing to the selective valorization of biomass. Our DFT calculations further validate that nickel sulfo-selenide demonstrates exceptional capabilities in adsorbing furfural and facilitating its efficient conversion to furoic acid through electrooxidation reactions. © 2025 Elsevier B.V.