Interfacial two-site synergy for biomass electro-oxidation in a near-neutral electrolyte

doi:10.1016/S1872-2067(26)65041-3

Abstract

Abstract:

Electrocatalytic oxidation of biomass-derived 5-hydroxymethylfurfural (HMF) in a near-neutral electrolyte mitigates HMF polymerization, thereby enhancing catalyst stability for long-term operation. However, the insufficient supply of active oxygen species during the electro-oxidation process often leads to the formation of partially oxidized intermediates instead of the desired product, 2,5-furandicarboxylic acid (FDCA). In this study, an atomically dispersed ruthenium-loaded copper oxide electrocatalyst (Ru/CuO) is prepared to promote the generation of hydroxide (OH^-) ions and facilitate complete HMF oxidation to FDCA. In-situ attenuated total reflectance surface-enhanced infrared absorption spectroscopy, density functional theory calculations, and quartz crystal microbalance mass analysis revealed that CuO serves as the active site for the HMF oxidation reaction (HMFOR), whereas the introduction of Ru single atoms accelerates OH^- formation, lowers the reaction barrier for the key dehydrogenation steps in HMFOR, and enhances HMF adsorption. These features enable the Ru/CuO catalyst to deliver significantly improved low-potential oxidation performance under near-neutral conditions, reaching a 93% FDCA yield and 87.7% Faradaic efficiency at 1.15 V_RHE, along with stable operation in a flow cell. This work demonstrates efficient conversion of HMF to FDCA in a near-neutral electrolyte and proposes a rational design strategy for HMFOR catalyst operating under near-neutral conditions.

Key words: 5-Hydroxymethylfurfural, Near-neutral electrolyte, Electrocatalysis, Electro-oxidation, 2,5-Furandicarboxylic acid

Chenyu Bu, Zhuoran Lu, Zhongcheng Xia, Yun Fan, Cairong Wang, Yutong Huang, Shuangyin Wang, Yuqin Zou. Interfacial two-site synergy for biomass electro-oxidation in a near-neutral electrolyte[J]. Chinese Journal of Catalysis, 2026, 86: 160-170.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(26)65041-3

https://www.cjcatal.com/EN/Y2026/V86/I7/160

Figures/Tables 4

Fig. 1. Physical and chemical properties of the Ru/CuO catalyst. (a) Representative HRTEM images of the Ru/CuO catalyst. (b) Representative HAADF-STEM image of the Ru/CuO catalyst; red circles indicate monodispersed Ru atoms. (c) Cu 2p XPS spectra of the Ru/CuO and CuO catalysts. XANES spectra of Ru K-edge (d) and Cu K-edge (e). FT-EXAFS spectra of Ru K-edge (f) and Cu K-edge (g). (h) Wavelet transform of the Ru/CuO, Ru foil, and RuO2.

Fig. 2. Electrochemical performances of the Ru/C, CuO, and Ru/CuO catalysts. (a) LSV curves of the Ru/C, CuO, and Ru/CuO catalysts for HMFOR with 50 mmol L-1 HMF. (b) LSV curves of the Ru/CuO catalyst in 0.5 mol L-1 KHCO3 with and without 50 mmol L-1 HMF. (c) HMF conversion and FDCA yield for 10 mmol L-1 HMFOR using the Ru/C, CuO, and Ru/CuO catalysts at 1.15 VRHE. (d) HMF conversion, yield, and FE of FDCA for the Ru/CuO catalyst at various potentials. (e) Required potential for the Ru/CuO and CuO catalysts to achieve 10 mA cm-2 in 0.5 mol L-1 KHCO3 and 1 mol L-1 KOH (Error bars: ± SD, n = 3). (f) LSV curves of the Ru/CuO and CuO catalysts in 0.5 mol L-1 KHCO3 with or without 50 mmol L-1 HMF in the flow electrolyzer (insert). (g) Stability test of the Ru/CuO catalyst in 1.0 mol L-1 KHCO3 with 150 mL of 20 mmol L-1 HMF at 50 mA.

Fig. 3. Potential HMFOR pathways in a neutral medium. Product quantitative analysis by HPLC during HMF electrolysis using the Ru/CuO (a) and CuO (b) catalysts at 1.15 VRHE. HMF evolution on the Ru/CuO (c) and CuO (d) catalysts, tracked by in-situ ATR-SEIRAS. (e) Possible HMFOR pathways in neutral and alkaline media and the associated rate-limiting steps.

Fig. 4. Mechanism underlying the enhanced HMFOR activity of the Ru/CuO catalyst in a neutral medium. In-situ ATR-SEIRAS spectra of the CuO (a) and Ru/CuO (b) catalysts at varying potential in a neutral medium. (c) CV curves of the Ru/CuO and CuO catalysts in 0.5 mol L-1 KHCO3. (d) OH- formation energy on the Ru/CuO and CuO catalysts. (e) QCM mass response of the Ru/CuO and CuO catalysts before and after the addition of 50 mmol L-1 HMF. (f) Adsorption energy of HMF on the Ru/CuO and CuO catalysts. (g) Energies of the HMF intermediates and transition states during HMFOR on the Ru/CuO and CuO surface based on DFT calculations.

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