在NO电还原中对和胺的结构敏感性的计算洞察
Pu Guo1, Dong Luan1, Huan Li1,2
1State Key Laboratory of Catalysis, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Zhongshan Road 457, Dalian 116023, P.R. China.
Journal of the American Chemical Society
|May 9, 2024
概括
在电催化氧化还原 (eNORR) 中,六角密封在氨生产中表现出色,而单原子催化剂则更喜欢胺. 催化剂结构极大地影响了反应的选择性.
科学领域:
- 电化学
- 催化剂
- 材料科学
背景情况:
- 电催化氧化还原 (eNORR) 对于化合物合成至关重要.
- 六角密封 (hcp) 对氨具有选择性,而面中心立方 (fcc) 和单原子催化剂 (Co-SAC) 具有不同的选择性.
研究的目的:
- 在eNORR中研究hcp-Co,fcc-Co和Co-SAC的结构敏感性.
- 阐明对氨和胺的选择性机制.
主要方法:
- 恒定电位模拟方法
- 微动力学模型
主要成果:
- 由于易于电子/质子转移和NO*抑制,hcp-Co对氨有更高的活性.
- 同SAC具有异常的胺选择性,归因于正电荷的活性中心和中度的NO吸附.
- 在hcp-Co和fcc-Co上,NOH*的形成更受青,而在Co-SAC上,HNO*更受青,这与NO吸附强度和方向有关.
结论:
- 在eNORR中,NO*质子化的第一步对于选择性控制至关重要.
- 催化剂局部和电子结构显著调节了eNORR中的活动和选择性.
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