原子隔离 Pd 站点通过质子调节机制促进电化学 CO 降解为乙酸
Shuying Li1, Gong Zhang1, Xiao Ma1
1School of Chemical Engineering & Technology, Key Laboratory for Green Chemical Technology of Ministry of Education, Collaborative Innovation Center for Chemical Science & Engineering (Tianjin), Tianjin University, Tianjin 300072, China.
铜纳米片上原子隔离的位增强了乙酸生产的电化学CO降解反应 (CORR). 这种策略优化了质子化步骤,实现了可持续化学合成的高选择性和稳定性.
科学领域:
- 电化学
- 材料科学
- 催化剂
背景情况:
- 电化学CO降解反应 (CORR) 是可持续酸盐生产的关键技术.
- 控制质子化步骤对于提高COR的选择性和效率至关重要.
- 现有的催化剂往往难以精确控制中间质子化路径.
研究的目的:
- 在铜 (Cu) 纳米片上合成原子隔离的 (Pd) 位.
- 研究这些Pd位点如何调节CORR中关键中间体的质子化.
- 通过CORR阐明选择性酸盐形成的机制.
主要方法:
- 在Cu纳米片上合成Pd位点.
- 包括动态同位素效应研究在内的电化学表征.
- 对中间质子和反应路径的分析.
- 在膜电极组件中进行长期稳定性测试.
主要成果:
- 具有中等水激活的Pd位点增强*CO质子转化为*COH,这是决定速度的步骤.
- Pd位点促进*COH-*CO中间体的形成.
- 在*COH-*CO中通过Pd位点的C-OH组的优先质子化导致*CCO的形成.
- 在0.78V与RHE相比达到59.5%的乙酸法拉代效率,在0.86V与RHE相比达到286mAcm-2的部分电流密度.
- 在100 mA cm-2下经过500小时的长期稳定性.
结论:
- 在Cu纳米片上原子隔离的Pd位点有效调节CORR中的质子.
- 这一策略通过控制中间路径来实现选择性酸盐形成.
- 这些发现揭示了通过催化剂结构和电子调整促进选择性CORR的新机制.
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