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Abstract <p>The molybdenum iron (Mo-Fe) cluster NaHFe<sub>2</sub>Mo<sub>2</sub>O<sub>8</sub>(OH)<sub>2</sub> was synthesized via a hydrothermal method at pH 7 in a glycolic acid/water mixed solvent. The addition of glycolic acid effectively prevented the instantaneous precipitation typically observed upon mixing molybdenum and iron salts. The neutral pH environment attenuated the ligand coordination capability, thereby inhibiting complex formation. At high temperature, the [MoO<sub>4</sub>] tetrahedra link to the columnar [FeO<sub>6</sub>] octahedral motifs&#xa0;<i>via</i>&#xa0;corner-sharing of three vertices to form a two-dimensional layered structure composed of alternating Mo–Fe oxide units. The Mo-Fe cluster demonstrated selective catalytic activity toward methanol oxidation to formaldehyde. The methanol conversion efficiency increased with temperature, reaching 50.72%, while formaldehyde selectivity remained stable within the range of 55.48–60.59%. However, the cluster demonstrated poor catalytic performance due to its low specific surface area and insufficient Mo/Fe ratio, which failed to counteract MoO<sub>3</sub> leaching during the reaction. Moreover, excess iron promoted complete methanol oxidation, further diminishing selectivity. Despite its current limitations for practical applications, the study provides a reference for designing and preparing mixed metal oxidic cluster catalysts.</p>

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Molybdenum Iron Cluster: Synthesis, Structure, and Selective Catalytic Performance for Methanol Oxidation

  • 期刊论文

  • 发表日期：

    2025年12月1日

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  • Siyuan Wang,
  • Jiazhi Wang,
  • Xinfang Wang,
  • Shuang Jin

摘要

Abstract

The molybdenum iron (Mo-Fe) cluster NaHFe2Mo2O8(OH)2 was synthesized via a hydrothermal method at pH 7 in a glycolic acid/water mixed solvent. The addition of glycolic acid effectively prevented the instantaneous precipitation typically observed upon mixing molybdenum and iron salts. The neutral pH environment attenuated the ligand coordination capability, thereby inhibiting complex formation. At high temperature, the [MoO4] tetrahedra link to the columnar [FeO6] octahedral motifs via corner-sharing of three vertices to form a two-dimensional layered structure composed of alternating Mo–Fe oxide units. The Mo-Fe cluster demonstrated selective catalytic activity toward methanol oxidation to formaldehyde. The methanol conversion efficiency increased with temperature, reaching 50.72%, while formaldehyde selectivity remained stable within the range of 55.48–60.59%. However, the cluster demonstrated poor catalytic performance due to its low specific surface area and insufficient Mo/Fe ratio, which failed to counteract MoO3 leaching during the reaction. Moreover, excess iron promoted complete methanol oxidation, further diminishing selectivity. Despite its current limitations for practical applications, the study provides a reference for designing and preparing mixed metal oxidic cluster catalysts.