Wang Wenke, Ji Dongfang, Sang Ting, Hao Jingcheng, Li Zhonghao, Zhang Xiaoyu
Key Laboratory of Colloid and Interface Chemistry, Ministry of Education, Shandong University, Jinan 250100, China.
Zhejiang Carbon Neutral Innovation Institute and Moganshan Institute of ZJUT at Deqing, Zhejiang University of Technology, Hangzhou 310014, China.
Inorg Chem. 2025 Jan 13;64(1):113-122. doi: 10.1021/acs.inorgchem.4c04324. Epub 2025 Jan 1.
The electrooxidation of 5-hydroxymethylfurfural (HMF) to 2,5-furandicarboxylic acid (FDCA) has been deeply investigated. However, developing a durable electrocatalyst for fast production of FDCA at low potentials remains a challenge. Herein, we report NiP-NiSe heterostructure nanosheet arrays as efficient electrocatalysts for HMF electrooxidation. These nanosheet arrays were synthesized via an in situ deep eutectic solvent etching approach, followed by phosphorization and a selenization process. The optimal NiP-NiSe electrocatalyst could achieve 99.1% FDCA selectivity, 98.9% Faradaic efficiency, and 100% HMF conversion at 1.38 V (reversible hydrogen electrode) within 1.6 h. Density functional theory calculations demonstrate that apparent charge redistribution occurs at the NiP/NiSe heterointerface, which greatly enhances HMF adsorption and consequently modulates the catalytic performance. In situ Raman spectroscopy technology confirms that NiOOH is the main active species during HMF electrooxidation. This work provides a significant strategy to develop robust heterogeneous electrocatalyst for HMF electrooxidation and beyond.
5-羟甲基糠醛（HMF）电氧化制备2,5-呋喃二甲酸（FDCA）已得到深入研究。然而，开发一种在低电位下快速生产FDCA的耐用电催化剂仍然是一项挑战。在此，我们报道了NiP-NiSe异质结构纳米片阵列作为HMF电氧化的高效电催化剂。这些纳米片阵列通过原位深共熔溶剂蚀刻法合成，随后进行磷化和硒化过程。最佳的NiP-NiSe电催化剂在1.38 V（可逆氢电极）下1.6小时内可实现99.1%的FDCA选择性、98.9%的法拉第效率和100%的HMF转化率。密度泛函理论计算表明，在NiP/NiSe异质界面处发生了明显的电荷重新分布，这大大增强了HMF的吸附，从而调节了催化性能。原位拉曼光谱技术证实，NiOOH是HMF电氧化过程中的主要活性物种。这项工作为开发用于HMF电氧化及其他领域的稳健非均相电催化剂提供了重要策略。
