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<p>The selective electrochemical oxidation of 5-hydroxymethylfurfural (HMF) to 2,5-furandicarboxylic acid (FDCA) holds transformative potential for advancing sustainable, bio-based polymer production. In this study, we unveil the pivotal role of gold single-crystal electrode surface orientation in directing HMF oxidation pathways under alkaline conditions. Using cyclic voltammetry, we systematically evaluate the oxidation behavior on Au(111), Au(100), Au(110), Au(311), Au(331), and Au(210) surfaces. Our findings reveal that Au(111) and Au(100) surfaces exhibit superior catalytic activity for the complete oxidation to FDCA, while Au(110) promotes the selective formation of 5-hydroxymethyl-2-furancarboxylic acid (HMFCA). These differences in activity are closely linked to the crystallographic structure, influencing adsorption energies and reaction intermediates. In situ infrared reflection absorption spectroscopy (IRRAS) and attenuated total reflectance (ATR) spectroscopy provide direct molecular insights, identifying distinct vibrational signatures of intermediates and products. This study highlights the critical role of electrode surface structure in tuning reaction efficiency and selectivity, contributing to the development of more efficient catalytic processes in green chemistry.</p>

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Insights into catalytic activity and selectivity of 5-Hydroxymethylfurfural oxidation on gold single-crystal electrodes

  • 期刊论文

  • 出版模式：

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  • 发表日期：

    2025年4月9日

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  • Lorena Chico-Mesa,
  • Antonio Rodes,
  • Rosa M. Arán-Ais,
  • Enrique Herrero

摘要

The selective electrochemical oxidation of 5-hydroxymethylfurfural (HMF) to 2,5-furandicarboxylic acid (FDCA) holds transformative potential for advancing sustainable, bio-based polymer production. In this study, we unveil the pivotal role of gold single-crystal electrode surface orientation in directing HMF oxidation pathways under alkaline conditions. Using cyclic voltammetry, we systematically evaluate the oxidation behavior on Au(111), Au(100), Au(110), Au(311), Au(331), and Au(210) surfaces. Our findings reveal that Au(111) and Au(100) surfaces exhibit superior catalytic activity for the complete oxidation to FDCA, while Au(110) promotes the selective formation of 5-hydroxymethyl-2-furancarboxylic acid (HMFCA). These differences in activity are closely linked to the crystallographic structure, influencing adsorption energies and reaction intermediates. In situ infrared reflection absorption spectroscopy (IRRAS) and attenuated total reflectance (ATR) spectroscopy provide direct molecular insights, identifying distinct vibrational signatures of intermediates and products. This study highlights the critical role of electrode surface structure in tuning reaction efficiency and selectivity, contributing to the development of more efficient catalytic processes in green chemistry.