Scholarlink

<p>Nickel-based materials can facilitate the electrocatalytic CO<sub>2</sub> reduction (CO<sub>2</sub>R) reaction to generate hydrocarbons up to C<sub>6</sub>. Here we show that fluorine doping alters the nature of the Ni active sites, which proves instrumental in tuning the selectivity of the CO<sub>2</sub>R. We interrogate the CO<sub>2</sub>R reaction mechanism using intermediate surrogates, including aldehydes, alkyl iodides and acetylene. Aldehydes are electroreduced to alcohols and deoxygenated intermediates. Among the latter, unsaturated hydrocarbon intermediates (RCH<sub>2−<i>x</i></sub>*, where the asterisk represents surface-bound species and <i>x</i> = 1 or 2) reacting with *CO dictate chain propagation, modulated by competitive C–C coupling and C–H hydrogenation reactions. Compound branching in the hydrocarbons initiates from *CO coupling with two *CH<sub>2</sub> species, and the branch-to-linear hydrocarbon ratio can be doubled using a pulsed potential strategy. An inverse H/D kinetic isotope effect promotes deuterated hydrocarbon formation with a Faradaic efficiency of 22.2%. This work reveals mechanisms and strategies for the conversion of CO<sub>2</sub> into linear and branched hydrocarbons, thus advancing electrosynthetic fuel development.</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

Controlling hydrocarbon chain growth and degree of branching in CO2 electroreduction on fluorine-doped nickel catalysts

  • 期刊论文

  • 发表日期：

    2025年7月17日

查看全文
  • Yingqing Ou,
  • Lu Liu,
  • Ranga Rohit Seemakurthi,
  • Futian You,
  • Haibin Ma,
  • Javier Pérez-Ramírez,
  • Núria López,
  • Boon Siang Yeo

摘要

Nickel-based materials can facilitate the electrocatalytic CO2 reduction (CO2R) reaction to generate hydrocarbons up to C6. Here we show that fluorine doping alters the nature of the Ni active sites, which proves instrumental in tuning the selectivity of the CO2R. We interrogate the CO2R reaction mechanism using intermediate surrogates, including aldehydes, alkyl iodides and acetylene. Aldehydes are electroreduced to alcohols and deoxygenated intermediates. Among the latter, unsaturated hydrocarbon intermediates (RCH2−x*, where the asterisk represents surface-bound species and x = 1 or 2) reacting with *CO dictate chain propagation, modulated by competitive C–C coupling and C–H hydrogenation reactions. Compound branching in the hydrocarbons initiates from *CO coupling with two *CH2 species, and the branch-to-linear hydrocarbon ratio can be doubled using a pulsed potential strategy. An inverse H/D kinetic isotope effect promotes deuterated hydrocarbon formation with a Faradaic efficiency of 22.2%. This work reveals mechanisms and strategies for the conversion of CO2 into linear and branched hydrocarbons, thus advancing electrosynthetic fuel development.