Scholarlink

<p>Understanding the hydrogenation pathway in electrochemical CO<sub>2</sub> reduction is important for controlling product selectivity. The Eley–Rideal mechanism involving proton-coupled electron transfer directly from solvent water is often considered to be the primary hydrogen transfer route. However, in principle, hydrogenation can also occur via the Langmuir–Hinshelwood mechanism using surface-adsorbed *H. Here, by performing CO<sub>2</sub> reduction with Cu in H<sub>2</sub>O–D<sub>2</sub>O mixtures, we present evidence that the Langmuir–Hinshelwood mechanism is probably the dominant hydrogenation route. From this, we estimate the extent to which each mechanism contributes towards the formation of six important CO<sub>2</sub> reduction products. Through computational simulations, we find that the formation of C–H bonds and O–H bonds is governed by the Langmuir–Hinshelwood and Eley–Rideal mechanism, respectively. We also show that promoting the Eley–Rideal pathway could be crucial towards selective multicarbon product formation and suppressing hydrogen evolution. These findings introduce important considerations for the theoretical modelling of CO<sub>2</sub> reduction pathways and electrocatalyst design.</p><p></p>

错误：搜索内容不能为空，请输入英文关键词
错误：关键词超出字数限制，请精简
高级检索

Isotopic labelling of water reveals the hydrogen transfer route in electrochemical CO2 reduction

  • 期刊论文

  • 发表日期：

    2025年2月6日

查看全文
  • Jiguang Zhang,
  • Chengyi Zhang,
  • Meng Wang,
  • Yu Mao,
  • Bo Wu,
  • Qin Yang,
  • Bingqing Wang,
  • Ziyu Mi,
  • Mingsheng Zhang,
  • Ning Ling,
  • Wan Ru Leow,
  • Ziyun Wang,
  • Yanwei Lum

摘要

Understanding the hydrogenation pathway in electrochemical CO2 reduction is important for controlling product selectivity. The Eley–Rideal mechanism involving proton-coupled electron transfer directly from solvent water is often considered to be the primary hydrogen transfer route. However, in principle, hydrogenation can also occur via the Langmuir–Hinshelwood mechanism using surface-adsorbed *H. Here, by performing CO2 reduction with Cu in H2O–D2O mixtures, we present evidence that the Langmuir–Hinshelwood mechanism is probably the dominant hydrogenation route. From this, we estimate the extent to which each mechanism contributes towards the formation of six important CO2 reduction products. Through computational simulations, we find that the formation of C–H bonds and O–H bonds is governed by the Langmuir–Hinshelwood and Eley–Rideal mechanism, respectively. We also show that promoting the Eley–Rideal pathway could be crucial towards selective multicarbon product formation and suppressing hydrogen evolution. These findings introduce important considerations for the theoretical modelling of CO2 reduction pathways and electrocatalyst design.