电催化氧降解反应的电催化反应由铜复合体与四牙三脚联体进行
Mathias L Skavenborg1,2, Mads Sondrup Møller1, Christopher J Miller2
1Department of Physics, Chemistry and Pharmacy, University of Southern Denmark, Odense M 5230, Denmark.
铜复合物与修改的tris(pyridin 2-ylmethyl) 胺 (tmpa) 连接体,具有碳酸盐捐赠体,有效催化水中的氧降解反应 (ORR). 这些新的配体为ORR电催化提供可调节的电子和结构性质.
科学领域:
- 协调化学 协调化学
- 电触媒溶解是一种电触媒.
- 绿色化学 绿色化学
背景情况:
- 四牙三脚体连接体支架对于稳定氧降解反应 (ORR) 催化中的铜离子至关重要.
- 通过引入碳酸盐供体来修改三二甲基胺 (tmpa) 支架,可以调整复合铜的电子和结构性质.
研究的目的:
- 研究用于ORR催化剂的铜复合体与含有碳酸盐供体的改性tmpa连接体的反应性.
- 探索连接物结构对水性介质中铜复合物的催化活性和电化学性能的影响.
主要方法:
- 用修改的TMPA连接体合成和表征铜复合物,包括二二甲基糖 (bpg) 和3-二二甲基氨基) 酸 (bpp).
- 在环中性水条件下对合成的复合物进行同质氧降解反应 (ORR) 催化的电化学评估.
- 确定氧化还原潜力和pKa值,以将连接体结构与催化性能相关联.
主要成果:
- 具有一个碳酸盐供体 (Cu-bpg和Cu-bpp) 的铜复合体在pH7的水中具有显著的电催化同质ORR活性.
- 对于Cu-bpg和Cu-bpp的周转频率与Cu-tmpa相似,范围为10^5到10^6s^-1.
- 在pH 7下,所有复合物都观察到类似的Cu (II) /Cu (I) 氧化还原潜力和溶液物种的整体+1电荷,通过易斯酸度和水合物相互作用进行合理化.
结论:
- 在tmppa支架中加入碳酸盐供体,为水性介质中的铜催化ORR提供有效的配体.
- 可调节的电子和结构特征,包括碳酸基组提供的H结合可能性,影响了催化活性.
- 这些发现突显了改造的tmpa连接体在环境相关条件下开发ORR高效和强大的电催化剂的潜力.
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