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<p>The electrochemical oxidation of 5-hydroxymethylfurfural (HMFOR) represents a promising route for biomass valorization, yet its efficiency is often limited by suboptimal adsorption configurations of reaction intermediates on conventional catalysts. Herein, we demonstrate that Ce doping effectively modulates both geometric and electronic structures of CuO to achieve exceptional HMFOR performance. The designed Ce-CuO catalyst exhibits remarkable activity and selectivity, achieving near-quantitative FDCA Faradaic efficiency (98.4%) with substantially enhanced production rates (67.0 µmol cm<sup>−2</sup> h<sup>−1</sup>) compared to pristine CuO (87.3%, 54.0 µmol cm<sup>−2</sup> h<sup>−1</sup>), while maintaining over 90% FDCA Faradaic efficiency over 8 cycles. Comprehensive <i>in-situ/ex-situ</i> spectroscopic characterization and theoretical calculations reveal that Ce incorporation induces electron transfer to Cu sites and triggers the coordination geometric restructuring, while simultaneously optimizing the geometric matching between active sites and reaction intermediates. This dual modulation enables key intermediates to adopt thermodynamically favorable adsorption configurations with significantly reduced steric hindrance, thereby lowering the energy barrier of the rate-determining step from 0.99 to 0.46 eV. This work establishes geometric configuration engineering through rational dopant incorporation as a crucial design strategy beyond conventional electronic structure modulation for advanced electrocatalysts in biomass conversion and other complex electrochemical transformations.</p>

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Ce-induced steric hindrance reduction in CuO for configuration matching in electrocatalytic 5-hydroxymethylfurfural oxidation

  • 期刊论文

  • 发表日期：

    2025年11月19日

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  • Xiangrui Wu,
  • Han Du,
  • Meng Li,
  • Lei Chen,
  • Dongan Liu,
  • Yingfan Jiang,
  • Wentao Xue,
  • Yu Wang,
  • Dongmei Sun,
  • Yawen Tang,
  • Gengtao Fu

摘要

The electrochemical oxidation of 5-hydroxymethylfurfural (HMFOR) represents a promising route for biomass valorization, yet its efficiency is often limited by suboptimal adsorption configurations of reaction intermediates on conventional catalysts. Herein, we demonstrate that Ce doping effectively modulates both geometric and electronic structures of CuO to achieve exceptional HMFOR performance. The designed Ce-CuO catalyst exhibits remarkable activity and selectivity, achieving near-quantitative FDCA Faradaic efficiency (98.4%) with substantially enhanced production rates (67.0 µmol cm−2 h−1) compared to pristine CuO (87.3%, 54.0 µmol cm−2 h−1), while maintaining over 90% FDCA Faradaic efficiency over 8 cycles. Comprehensive in-situ/ex-situ spectroscopic characterization and theoretical calculations reveal that Ce incorporation induces electron transfer to Cu sites and triggers the coordination geometric restructuring, while simultaneously optimizing the geometric matching between active sites and reaction intermediates. This dual modulation enables key intermediates to adopt thermodynamically favorable adsorption configurations with significantly reduced steric hindrance, thereby lowering the energy barrier of the rate-determining step from 0.99 to 0.46 eV. This work establishes geometric configuration engineering through rational dopant incorporation as a crucial design strategy beyond conventional electronic structure modulation for advanced electrocatalysts in biomass conversion and other complex electrochemical transformations.