作为催化水氧化中的氧化继电器的碳酸盐连接体
Shaoqi Zhan1, Juan Angel De Gracia Triviño1, Mårten S G Ahlquist1
1Department of Theoretical Chemistry & Biology, School of Engineering Sciences in Chemistry Biotechnology and Health , KTH Royal Institute of Technology , 10691 Stockholm , Sweden.
Journal of the American Chemical Society
|June 14, 2019
概括
在催化剂中使用碳酸盐组的新型"氧化继电"机制显著增强了水的氧化. 这种功能促进了关键的O-O键形成和核友攻击,为下一代催化剂铺平了道路.
科学领域:
- 催化剂
- 材料科学
- 计算化学
背景情况:
- 碳酸盐组在过渡金属催化剂配体中很常见.
- 它们在水氧化催化中的作用仅限于传统功能.
研究的目的:
- 介绍一种新的催化碳酸盐组机制:氧化继电器.
- 研究这种氧化继电器在Ru (tda) (py) 2水氧化催化剂中的作用.
主要方法:
- 实证价值键-分子动力学 (EVB-MD) 用于键形成.
- 分子动力学 (MD) 模拟扩散和结合的自由能量.
- 密度函数理论 (DFT) 用于激活自由能量.
主要成果:
- 氧化继电器促进了O-O键的形成和核友的攻击.
- 计算的周转频率与不同pH值的实验数据保持一致.
- 确定的速度限制步骤从核友性攻击 (低pH) 转变为O-O键形成 (高pH).
结论:
- 氧化物继电器是催化剂高效率的关键.
- 这种机制可以激发先进的水氧化催化剂的设计.
- 建议进行进一步的同位素实验以验证拟议的机制.
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