在生物启发的H2生产电催化剂中作为质子穿的Hemilabile桥梁Thiolates
Shengda Ding1, Pokhraj Ghosh1, Allen M Lunsford1
1Department of Chemistry, Texas A & M University , College Station, Texas 77843, United States.
Journal of the American Chemical Society
|August 20, 2016
概括
研究人员在电催化剂中探索了质子-电子和质子-合物. Ni-Fe和Fe-Fe复合物表现出活性,其机制涉及金属-硫键裂变和有效合的特定方向.
科学领域:
- 无机化学
- 电催化
- 生物有机化学
背景情况:
- 酶对生物代谢至关重要.
- 合成类似物旨在模仿电催化剂的酶活性位点.
- 了解质子-电子和质子-合物是高效生产H2的关键.
研究的目的:
- 研究合成电催化剂中控制质子-电子和质子-合物的特征.
- 探索由[NiFe]-酶启发的双金属复合物的结构功能关系.
- 确定生产H2的活性电催化剂并阐明它们的反应机制.
主要方法:
- 合成与铁组成部分聚合的双金属dithiolato复合物 (MN2S2).
- 电化学分析以确定生产H2的催化活性.
- 计算研究以与机械参数相关联的电化学潜力.
主要成果:
- 确定了Ni-Fe'和Fe-Fe'双金属复合物作为H2生产的活性电催化剂.
- 该机制涉及用于电子吸收和Fe-S键裂解的氧化还原活性NO配体 (hemilability).
- 有效的合需要特定的化物和质子,以形成H2,这取决于氧化还原水平.
结论:
- 非无害的NO连接体在电子储存中起作用,而不是化物形成.
- 铁-S键裂变和硫酸盐溶解性对于质子转运和H2生成至关重要.
- 催化剂的稳定性受金属组成和不必要的键裂变 (例如Fe'-S) 的可能性的影响.
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