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<p>Future practical applications of the electrochemical CO<sub>2</sub> reduction reaction will probably involve the use of higher pressures and temperatures. However, most research on the copper-catalysed electrochemical CO<sub>2</sub> reduction reaction—the most widely studied system due to its C–C coupling ability—is typically performed under ambient conditions, and hence the mechanistic conclusions drawn also pertain to those conditions. Using a custom high-pressure, high-temperature electrochemical cell, we show here that on copper electrodes, the C–C coupling mechanism changes from the typical CO dimerization mechanism at low temperatures to a Fischer–Tropsch-like chain growth mechanism at temperatures above 125 °C (also requiring higher pressure). These results show that temperature and pressure are crucial parameters to consider in applied and mechanistic studies of the electrochemical reduction of CO<sub>2</sub> because they can open up alternative reaction pathways and alter known mechanisms.</p><p></p>

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CO2 electroreduction on Cu operates via an alternative chain growth mechanism to form C–C bonds at elevated temperature and pressure

  • 期刊论文

  • 出版模式：

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  • 发表日期：

    2025年12月12日

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  • Rafaël E. Vos,
  • Pengfei Sun,
  • Daniel Schauermann,
  • Hassan Javed,
  • Selwyn R. Hanselman,
  • Gang Fu,
  • Marc T. M. Koper

摘要

Future practical applications of the electrochemical CO2 reduction reaction will probably involve the use of higher pressures and temperatures. However, most research on the copper-catalysed electrochemical CO2 reduction reaction—the most widely studied system due to its C–C coupling ability—is typically performed under ambient conditions, and hence the mechanistic conclusions drawn also pertain to those conditions. Using a custom high-pressure, high-temperature electrochemical cell, we show here that on copper electrodes, the C–C coupling mechanism changes from the typical CO dimerization mechanism at low temperatures to a Fischer–Tropsch-like chain growth mechanism at temperatures above 125 °C (also requiring higher pressure). These results show that temperature and pressure are crucial parameters to consider in applied and mechanistic studies of the electrochemical reduction of CO2 because they can open up alternative reaction pathways and alter known mechanisms.