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<p>The proton-coupled electron transfer (PCET) kinetics plays a critical role in governing the CO<sub>2</sub>-to-formate conversion efficiency during CO<sub>2</sub> eletroreduction reaction. While alkali metal cations are known to influence the reaction pathway, elucidating how trace doping modifies the catalytic sites remains a key challenge. Here we show that incorporating Li into bismuth oxycarbonate (BOC-Li) induces structural modifications that optimize the PCET process at bismuth-active sites, thereby boosting CO<sub>2</sub>-to-formate conversion. By employing dual-isotope (<sup>2</sup>H/<sup>13</sup>C) operando nuclear magnetic resonance&#xa0;(NMR) to track the formation of <sup>1</sup>H<sup>13</sup>COO<sup>−</sup>/<sup>2</sup>H<sup>13</sup>COO<sup>−</sup>, combined with kinetic isotope effect, Tafel analysis and in situ attenuated total reflection surface-enhanced infrared absorption spectroscopy, we observe a more efficient proton-electron transfer pathway. Density functional theory (DFT) calculations suggest that Li doping is associated with enhanced activity of Bi sites, potentially strengthening H<sub>2</sub>O/CO<sub>2</sub> adsorption and reducing the O–H activation energy. Collectively, this work highlights alkali doping as a promising strategy for structurally engineering catalytic sites to improve PCET kinetics.</p>

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Operando nuclear magnetic resonance decodes alkali-tuned proton-electron relay boosting CO2-to-formate conversion

  • 期刊论文

  • 出版模式：

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  • 发表日期：

    2026年1月20日

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  • Yingli Shi,
  • Ying Liu,
  • Hongchun Dong,
  • Gaocheng Fu,
  • Hang Zhou,
  • Haifeng Wang,
  • Xue-Lu Wang,
  • Ye-Feng Yao

摘要

The proton-coupled electron transfer (PCET) kinetics plays a critical role in governing the CO2-to-formate conversion efficiency during CO2 eletroreduction reaction. While alkali metal cations are known to influence the reaction pathway, elucidating how trace doping modifies the catalytic sites remains a key challenge. Here we show that incorporating Li into bismuth oxycarbonate (BOC-Li) induces structural modifications that optimize the PCET process at bismuth-active sites, thereby boosting CO2-to-formate conversion. By employing dual-isotope (2H/13C) operando nuclear magnetic resonance (NMR) to track the formation of 1H13COO−/2H13COO−, combined with kinetic isotope effect, Tafel analysis and in situ attenuated total reflection surface-enhanced infrared absorption spectroscopy, we observe a more efficient proton-electron transfer pathway. Density functional theory (DFT) calculations suggest that Li doping is associated with enhanced activity of Bi sites, potentially strengthening H2O/CO2 adsorption and reducing the O–H activation energy. Collectively, this work highlights alkali doping as a promising strategy for structurally engineering catalytic sites to improve PCET kinetics.