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由铁 (II) 复合体中的双酸N-异环的异原子驱动的进化
Soma Keszei1,2, Yiqing Wang3, Haotian Zhou3
1Centre for Energy Research, Institute of Technical Physics and Materials Science, H-1121, Konkoly-Thege út 29-33, Budapest, Hungary. keszei.soma@ek.hun-ren.hu.
Dalton transactions (Cambridge, England : 2003)
|August 22, 2024
概括
本研究探讨了用于演化反应 (HER) 的非贵金属催化剂. 具有特定连接体的铁复合体显示出有前途的HER活性,与连接体结构和电子特性相关.
科学领域:
- 电化学 电化学 电化学
- 催化剂是一种催化剂.
- 无机化学 无机化学
背景情况:
- 是演化反应 (HER) 的基准催化剂,但成本和稀缺性需要探索非贵金属替代品.
- 非贵金属复合物的催化活性高度依赖于连接体的电子和结构性质,特别是结合点的性质.
研究的目的:
- 为了研究双联体中非协调性异构原子 (S,O,N) 对Fe (II) 复合物的电催化演化反应 (HER) 活性的影响.
- 为了将HER性能与连接物基本性,电子结构和机械路径相关联.
主要方法:
- 合成和表征Fe(II) 复合物与2-(2'-pyridyl) -benzoxazole (LO),2-(2'-pyridyl) -benzthiazole (LS),2-(2'-pyridyl) -benzimidazole (LNH) 和2-2'-bipyridyl (Lpy) 连接物.
- 电化学研究包括循环电压测量和使用三酸 (TFA) 作为质子源的受控电位电解.
- 密度函数理论 (DFT) 计算以探测电子结构和反应机制.
主要成果:
- 在TFA的存在下,HER的降低潜力与带基本性相关.
- DFT的计算揭示了基于联体的LUMO和LUMO+1轨道中电荷分布的重要性.
- 对于具有LNH,LO和LS连接体的复合体,分别观察到0.03,1.1和10.8s^-1的HER活动 (k_obs).
- 活动与[Fe ((LS/O/NH) 2 ((S) 2+) ]2+物种有关,其中率决定步骤涉及Fe-H和TFA键的削弱.
结论:
- 配体中的非协调性异构原子显著影响Fe (II) 复合体的HER活性.
- 连接物基本性和电子结构,特别是边界轨道中的电荷分布,是有效的HER催化的主要因素.
- 含有LS,LO和LNH联体的Fe (II) 复合物代表了 HER.的有希望的非贵金属电催化剂.
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