对Ag-Imidazole立方体微环境的阳离子调节,以有效地减少电催化CO2
Wenqian Yang1, Qijie Mo1, Qi-Ting He1
1MOE Laboratory of Bioinorganic and Synthetic Chemistry, GBRCE for Functional Molecular Engineering, LIFM, IGCME, School of Chemistry, Sun Yat-Sen University, 510275, Guangzhou, China.
我们开发了基于银的新金属有机 (Ag-MOCs),以有效地将二氧化碳电还原为一氧化碳 (CO). Ag-MOC-NO3催化剂在各种pH水平上表现出高的CO选择性.
科学领域:
- 材料科学 材料科学 材料科学
- 电化学 电化学 电化学
- 超分子化学 超分子化学
背景情况:
- 有效的电催化二氧化碳减排对于可持续的化学品生产至关重要.
- 金属有机 (MOCs) 为催化提供可调节的活性点和微环境.
- 了解二氧化碳电还原的机制仍然是一个挑战.
研究的目的:
- 设计和合成新的Ag-MOCs,以实现高效的二氧化碳电还原.
- 研究MOC结构和离子类型在催化性能中的作用.
- 为了阐明二氧化碳转化为二氧化碳的反应机制.
主要方法:
- 自组装Ag4L4立方体,使用Ag+离子和三角形伊米达基连接体.
- 在pH-通用电解质中对Ag-MOC-X催化剂 (X=NO3,ClO4,BF4) 进行电化学测试.
- 在现场减弱的总反射里埃变换红外光谱学 (ATR-FTIR) 用于中间检测.
- 密度函数理论 (DFT) 计算以探测反应机制.
主要成果:
- Ag-MOC-NO3表现出高的二氧化碳相应效率 (86.1%的酸性,94.1%的中性,95.3%的性).
- 催化性能与不同的对抗离子 (NO3 > ClO4 > BF4) 有显著的差异.
- ATR-FTIR证实了*COOH中间体的形成.
- DFT的计算显示,二氧化碳吸附在不和的Ag位点上,这些位点通过结和离子调节的Ag中心动态稳定.
结论:
- 农业MOCs为高效的二氧化碳电还原提供了一个有希望的超分子平台.
- 阳离子模板效应和Ag-协调几何学极大地影响了催化活性.
- 这项工作提供了一个设计MOC作为CO2转换的高性能电催化剂的策略.
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