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Subsurface engineering for directional-selective CO₂-to-ethanol electrocatalysis at industrial-level.

Ming-Zheng Gu1, Yuan Min2, Ling Jiang1

  • 1Key Laboratory of Functional Molecular Solids, Ministry of Education, Anhui Key Laboratory of Molecule-Based Materials, Anhui Engineering Research Center of Carbon Neutrality, College of Chemistry and Materials Science, Anhui Normal University, Wuhu, Anhui, China.

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|December 6, 2025
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A new subsurface cobalt-doped copper sulfide (Co-Sub-CuS) catalyst enhances selectivity for electroreduction of carbon dioxide (CO2) to ethanol. This catalyst improves intermediate conversion and C-C coupling for efficient and stable ethanol production.

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Area of Science:

  • Electrochemistry
  • Catalysis
  • Materials Science

Background:

  • Controlling selectivity in CO2 electroreduction to ethanol is challenging due to intermediate adsorption.
  • The branching pathway following C-C coupling limits directed selectivity.

Purpose of the Study:

  • To develop a catalyst for directed selectivity in CO2 electroreduction to ethanol.
  • To elucidate the mechanism of subsurface doping in enhancing catalyst performance.

Main Methods:

  • Synthesis of subsurface Co-doped CuS (Co-Sub-CuS) catalyst.
  • Theoretical calculations and in-situ isotopic spectroscopy.
  • Electrochemical testing in a membrane electrode assembly electrolyzer.

Main Results:

  • Co-Sub-CuS exhibits directed selectivity toward ethanol.
  • Subsurface doping enhances oxophilicity and facilitates intermediate conversion via surface-O bonds.
  • Surface sulfur vacancies regulate dual-site distance for asymmetric C-C coupling.
  • Achieved 78.7% ethanol Faradaic efficiency at 550.9 mA cm⁻² and 305 h stability at 700 mA cm⁻².

Conclusions:

  • Subsurface doping provides a rational design strategy for selective CO2 electroreduction catalysts.
  • The Co-Sub-CuS catalyst demonstrates high efficiency and stability for ethanol production.
  • Understanding intermediate conversion pathways is crucial for catalyst development.