Self-Reconstruction of Sulfate-Terminated Copper Oxide Nanorods for Efficient and Stable 5-Hydroxymethylfurfural Electrooxidation

Ziyi Fan; Qianqian Yang; Wenjun Zhang; Huiming Wen; Haiyang Yuan; Jing He; Hua Gui Yang; Zupeng Chen

doi:10.1021/acs.nanolett.3c03949

Self-Reconstruction of Sulfate-Terminated Copper Oxide Nanorods for Efficient and Stable 5-Hydroxymethylfurfural Electrooxidation

Nano Lett. 2023 Dec 13;23(23):11314-11322. doi: 10.1021/acs.nanolett.3c03949. Epub 2023 Nov 29.

Authors

Ziyi Fan¹, Qianqian Yang², Wenjun Zhang¹, Huiming Wen¹, Haiyang Yuan², Jing He³, Hua Gui Yang², Zupeng Chen¹

Affiliations

¹ Jiangsu Co-Innovation Center of Efficient Processing and Utilization of Forest Resources, International Innovation Center for Forest Chemicals and Materials, College of Chemical Engineering, Nanjing Forestry University, Longpan Road 159, Nanjing 210037, China.
² Key Laboratory for Ultrafine Materials of Ministry of Education, Shanghai Engineering Research Center of Hierarchical Nanomaterials, School of Materials Science and Engineering, East China University of Science and Technology, 130 Meilong Road, 200237, Shanghai, China.
³ State Key Laboratory of Chemical Resource Engineering, Beijing University of Chemical Technology, Beijing, 100029, China.

PMID: 38018816
DOI: 10.1021/acs.nanolett.3c03949

Abstract

The electrochemical 5-hydroxymethylfurfural oxidation reaction (HMFOR) has been regarded as a viable alternative to sustainable biomass valorization. However, the transformation of the catalysts under harsh electrooxidation conditions remains controversial. Herein, we confirm the self-construction of cuprous sulfide nanosheets (Cu₂S NSs) into sulfate-terminated copper oxide nanorods (CuO-SO₄^2- NRs) during the first-cycle of the HMFOR, which achieves a near-quantitative synthesis of 2,5-furandicarboxylic acid (FDCA) with a >99.9% yield and faradaic efficiency without deactivation in 15 successive cycles. Electrochemical impedance spectroscopies confirm that the surface SO₄^2- effectively reduces the onset potential for HMFOR, while in situ Raman spectroscopies identify a reversible transformation from Cu^II-O to Cu^III-OOH in HMFOR. Furthermore, density functional theory calculations reveal that the surface SO₄^2- weakens the Cu-OH bonds in CuOOH to promote the rate-determining step of its coupling with the C atom in HMF-H* resulting from HMF hydrogenation, which synergistically enhances the catalytic activity of CuO-SO₄^2- NRs toward HMF-to-FDCA conversion.

Keywords: 2,5-furandicarboxylic acid; 5-hydroxymethylfurfural oxidation; biomass valorization; electrooxidation; self-reconstruction.