当地协调微环境在调节由基于Cr的单原子催化剂催化的CO2电还原中的重要性
Lei Yang1, Bin Li1, Ruo-Ya Wang1
1School of Chemistry and Chemical Engineering, Guizhou University, Guiyang 550025, China.
Journal of colloid and interface science
|May 16, 2025
概括
本研究介绍了一种基于的新型单原子催化剂 (Cr-N4-Cz),用于有效减少二氧化碳 (CO2RR). 催化剂上的原子置换显著提高了选择性,并抑制了竞争中的进化反应 (HER).
科学领域:
- 电化学 电化学 电化学
- 材料科学 材料科学 材料科学
- 计算化学计算化学
背景情况:
- 具有MN4活性位点的单原子催化剂 (SAC) 对二氧化碳还原反应 (CO2RR) 是有前途的.
- 基于Corrol的配体提供了一个调整SACs中活跃中心微环境的模型.
研究的目的:
- 为CO2RR.设计和研究一种基于Corrol的新型SAC,Cr-N4-Cz,用于CO2RR.
- 探索地方协调微环境修改如何影响催化活性和选择性.
- 使用DFT计算,阐明CO2RR和竞争演化反应 (HER) 的机制.
主要方法:
- 使用密度函数理论 (DFT) 的计算.
- 评估了各种Cr-N3X-Cz (X = N,C,O,S,P) 配置的稳定性.
- 研究了CO2RR和HER的机制,以了解选择性控制.
主要成果:
- Cr-N4-Cz表现出高的CO2RR活性 (限制潜力为-0.25V),有利于CO的产生.
- 竞争性HER (限制潜力为-0.28V) 降低了CO2RR的选择性.
- 原子替代 (C,O,S,P) 将产品改变为HCOOH,CO和CH3OH/CH4,抑制HER,并增加CO2RR选择性.
- 替代显著改善了电荷转移,促进了CH3OH/CH4的形成.
结论:
- 基于Corrol的SAC中的原子替代是一种有效的策略,用于调整微环境并增强CO2RR选择性.
- DFT计算提供了对该机制的洞察,突出了d轨道稳定和电荷转移的作用.
- 开发的Cr-N4-Cz催化剂及其衍生品显示出选择性电化学CO2转换的潜力.
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