Shuaiqin Huang, Huan Wen, Shuyi Zheng, Zelong Sun, Junxin Chen, Zhangyue Zheng, Jia Wu*, Shibin Yin*

Cite this article: Chin. J. Struct. Chem., 2025, 44(11), 100697. DOI: 10.1016/j.cjsc.2025.100697

Publication date: November 1, 2025

Keywords: 5-Hydroxymethylfurfural oxidation; 2,5-Furandicarboxylic acid; NiMo alloy; Ni³⁺; MoO₄²⁻

ABSTRACT

NiMo catalyst exhibits excellent catalytic performance in the electrooxidation of 5-hydroxymethylfurfural (HMF) to produce high-value 2,5-furandicarboxylic acid (FDCA). Although metallic nickel is known to undergo reconstruction into high-valent species during the reaction, the dynamic evolution of molybdenum components in NiMo catalyst and their mechanistic roles in the catalytic reaction remain unclear. In this study, the structural evolution of NiMo alloy during HMF electrooxidation is systematically investigated. Operando analyses reveal that under anodic polarization, molybdenum undergoes oxidative dissolution in the form of MoO42‒, concurrently driving the generation of high-valent Ni3+ species. Meanwhile, the dissolved MoO42‒ re-adsorbs on the catalyst surface, forming a unique interfacial structure with Ni3+. Electrochemical results demonstrate that this surface structure facilitates a synergistic effect between the MoO42‒ and high-valent Ni3+, enhancing the adsorption and activation of HMF molecules. Therefore, NiMo alloy exhibits excellent catalytic performance, with a high FDCA selectivity of 99.0%. This study provides new insights into the relationship between the catalyst reconstruction process and enhancement of catalytic performance.