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<p>Cu-based catalysts show significant potential in the selective hydrogenation of dimethyl oxalate (DMO) to methyl glycolate (MG). However, strong MG adsorption often induces over-hydrogenation, limiting their practical applicability. In this study, a hydroxyapatite (HAP)-modified Cu/SiO<sub>2</sub> catalyst was developed, achieving an MG yield of 91.73%. Structural and surface analyses show that the SiO<sub>2</sub>-HAP composite support constructs a balanced acid-base microenvironment, while the interaction between PO<Stack> <sub>4</sub> <sup>3−</sup> </Stack> groups and Si-OH induces mild lattice expansion and forms Cu-O-P linkages. These structural features stabilize dispersed Cu nanoparticles and help maintain an appropriate Cu<sup>+</sup>/Cu<sup>0</sup> ratio that supports C=O activation and H<sub>2</sub> dissociation. The coexistence of Si-OH acidic sites and PO<Stack> <sub>4</sub> <sup>3−</sup> </Stack> basic sites creates a balanced adsorption-desorption behavior. Acidic sites stabilize MG intermediates, while basic sites promote timely desorption and suppress deep hydrogenation to ethylene glycol. With coordinated Cu sites and acid-base synergy, the catalyst achieves high MG selectivity, offering a feasible route for noble-metal-free Cu systems.</p>

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Hydroxyapatite-modulated acid-base properties of Cu-based catalysts for enhanced selective methyl glycolate synthesis

  • 期刊论文

  • 发表日期：

    2026年6月18日

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  • Zhanpeng Xu,
  • Fangjun Shao,
  • Wei Huang,
  • Shaokang Zheng,
  • Lintao Rui,
  • Xu Zhang,
  • Hongbin Liao,
  • Jianguo Wang

摘要

Cu-based catalysts show significant potential in the selective hydrogenation of dimethyl oxalate (DMO) to methyl glycolate (MG). However, strong MG adsorption often induces over-hydrogenation, limiting their practical applicability. In this study, a hydroxyapatite (HAP)-modified Cu/SiO2 catalyst was developed, achieving an MG yield of 91.73%. Structural and surface analyses show that the SiO2-HAP composite support constructs a balanced acid-base microenvironment, while the interaction between PO 4 3− groups and Si-OH induces mild lattice expansion and forms Cu-O-P linkages. These structural features stabilize dispersed Cu nanoparticles and help maintain an appropriate Cu+/Cu0 ratio that supports C=O activation and H2 dissociation. The coexistence of Si-OH acidic sites and PO 4 3− basic sites creates a balanced adsorption-desorption behavior. Acidic sites stabilize MG intermediates, while basic sites promote timely desorption and suppress deep hydrogenation to ethylene glycol. With coordinated Cu sites and acid-base synergy, the catalyst achieves high MG selectivity, offering a feasible route for noble-metal-free Cu systems.