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<p>Replacing the oxygen evolution reaction with the electrocatalytic oxidation of glycerol to formic acid offers an attractive route for value-added chemical production. Spinel-type oxides, recognized for their favorable electronic structures, are active for GOR; however, monometallic spinels typically exhibit suboptimal performance due to insufficient substrate enrichment at the catalyst interface. In this study, a three-dimensional heterojunction catalyst (CoFe<sub>2</sub>O<sub>4</sub>/MnCo<sub>2</sub>O<sub>4</sub>) was grown on nickel foam via a simple hydrothermal and calcination method. The CoFe<sub>2</sub>O<sub>4</sub>/MnCo<sub>2</sub>O<sub>4</sub> heterojunction exhibits outstanding electrocatalytic performance toward direct glycerol oxidation, achieving a Faradaic efficiency for formic acid of up to 90% and a low potential of only 1.299&#xa0;V vs. RHE at a current density of 100&#xa0;mA·cm<sup>−2</sup>. Moreover, the GOR exhibits a 200&#xa0;mV lower potential at 200&#xa0;mA·cm<sup>−2</sup> compared to the oxygen evolution reaction (OER), substantially reducing the reaction voltage and energy consumption. The interfacial synergy within the heterojunction facilitates efficient charge transfer, enhances the adsorption of glycerol, and lowers the reaction overpotential, thereby accelerating the overall reaction kinetics. This work not only enables the selective synthesis of high-value chemicals but also offers an in-depth analysis of the catalyst's structure–performance relationship, paving a new avenue for the rational design of highly efficient heterogeneous catalysts.</p> Graphical Abstract <p>The spinel heterojunction creates a synergistic effect that enhances reactant adsorption, facilitates charge transfer, and lowers the overpotential, resulting in highly selective formic acid production with 90% Faradaic efficiency and significantly reduced energy consumption compared to OER.</p> <p></p>

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Synergistic interface in CoFe2O4/MnCo2O4 heterojunction for efficient electrocatalytic glycerol oxidation to formic acid

  • 期刊论文

  • 发表日期：

    2026年6月3日

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  • Yin Gao,
  • Honghui Ning,
  • Changjian Luo,
  • Yan Chen,
  • Jiaye Lan,
  • Yurong Shen,
  • Huaizhi Liu,
  • Rui Yang

摘要

Replacing the oxygen evolution reaction with the electrocatalytic oxidation of glycerol to formic acid offers an attractive route for value-added chemical production. Spinel-type oxides, recognized for their favorable electronic structures, are active for GOR; however, monometallic spinels typically exhibit suboptimal performance due to insufficient substrate enrichment at the catalyst interface. In this study, a three-dimensional heterojunction catalyst (CoFe2O4/MnCo2O4) was grown on nickel foam via a simple hydrothermal and calcination method. The CoFe2O4/MnCo2O4 heterojunction exhibits outstanding electrocatalytic performance toward direct glycerol oxidation, achieving a Faradaic efficiency for formic acid of up to 90% and a low potential of only 1.299 V vs. RHE at a current density of 100 mA·cm−2. Moreover, the GOR exhibits a 200 mV lower potential at 200 mA·cm−2 compared to the oxygen evolution reaction (OER), substantially reducing the reaction voltage and energy consumption. The interfacial synergy within the heterojunction facilitates efficient charge transfer, enhances the adsorption of glycerol, and lowers the reaction overpotential, thereby accelerating the overall reaction kinetics. This work not only enables the selective synthesis of high-value chemicals but also offers an in-depth analysis of the catalyst's structure–performance relationship, paving a new avenue for the rational design of highly efficient heterogeneous catalysts.

Graphical Abstract

The spinel heterojunction creates a synergistic effect that enhances reactant adsorption, facilitates charge transfer, and lowers the overpotential, resulting in highly selective formic acid production with 90% Faradaic efficiency and significantly reduced energy consumption compared to OER.