Pt/a-C纳米材料电催化2，5-呋喃二甲醇选择性氧化合成2，5-呋喃二甲酸

Electrocatalytic Selective Oxidation of 2，5-Bis（hydroxymethyl）furan to 2，5-Furandicarboxylic Acid over Pt/a-C Nanomaterials

摘要

2，5-呋喃二甲酸（FDCA）作为一种关键的生物质基平台化合物， 其绿色合成备受关注. 本文以稳定性优于5-羟甲基糠醛（HMF）的2，5-呋喃二甲醇（BHMF）为原料， 采用Pt/非晶碳（Pt/a-C）纳米材料为催化剂， 在温和条件下（1.45 V vs. RHE， 常温常压）实现了BHMF高效电催化氧化制备FDCA. 结果表明， Pt以纳米线形式通过Pt—C键均匀负载于非晶碳载体， 形成强界面相互作用； Pt/a-C的起始电位较商业Pt/C负移220 mV， Tafel斜率为34.63 mV/dec， 电荷转移电阻显著降低. 在1.45 V（vs. RHE）电位下， FDCA产率达92.80%， 法拉第效率为91.45%， 且循环5次后性能保持稳定. 机理研究揭示， 反应遵循双路径并行机制： BHMF经2，5-呋喃二甲醛（DFF）或5-羟甲基-2-呋喃甲酸（HMFCA）两条路径， 最终通过5-甲酰基-2-呋喃甲酸（FFCA）转化为FDCA， Pt活性中心与载体的协同作用促进了反应动力学.

Abstract

2,5-Furandicarboxylic acid（FDCA）, as a key biomass-derived platform chemical, has attracted considerable attention for its green synthesis. In this study, 2,5-bis（hydroxymethyl）furan（BHMF）, which exhibits higher stability than 5-hydroxymethylfurfural（HMF）, was used as the feedstock. Pt/amorphous carbon（Pt/a-C） nanomaterials were employed as the catalyst to achieve efficient electrocatalytic oxidation of BHMF to FDCA under mild conditions（1.45 V vs. RHE, room temperature and ambient pressure）. The results show that Pt nanowires are uniformly loaded onto the amorphous carbon support via Pt-C bonds, forming a strong interfacial interaction. Pt/a-C exhibits a 220 mV negative shift in onset potential compared to commercial Pt/C, with a Tafel slope of 34.63 mV/dec and a significantly reduced charge transfer resistance. At an applied potential of 1.45 V（vs. RHE）, the FDCA yield reached 92.80% with a Faradaic efficiency of 91.45%, and the performance remains stable after five cycles. Mechanistic investigation reveals that the reaction follows a dual-pathway parallel mechanism： BHMF is converted FDCA via either 2,5-diformylfuran（DFF） or 5-hydroxymethyl-2-furancarboxylic acid（HMFCA）, both ultimately proceeding through 5-formyl-2-furancarboxylic acid（FFCA） to FDCA. The synergistic effect between the Pt active sites and the support promotes the reaction kinetics. This study provides a new strategy for the green synthesis of biomass-based FDCA.

关键词

2，5-呋喃二甲醇 / 2，5-呋喃二甲酸 / 电催化氧化 / Pt/非晶碳 / 生物质高值化

Key words

2,5-Bis（hydroxymethyl）furan / 2,5-Furandicarboxylic acid / Electrocatalytic oxidation / Pt/amorphous carbon / High-value utilization of biomass

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基金资助

东华工程科技股份有限公司研发项目(W2023JSKF0971)

安徽省自然科学基金(JZ2024AKZR0546)