在金属有机框架的邻近分子中通过素离子调节3d电荷状态,以改善水氧化
Yitian Hu1,2, Yalei Fan1, Lili Li3
1Key Laboratory of Interfacial Physics and Technology, Shanghai Institute of Applied Physics, Chinese Academy of Sciences, Shanghai, 201800, China.
Small (Weinheim an der Bergstrasse, Germany)
|April 11, 2024
概括
在金属有机框架 (MOF) 中引入素效应可以增强氧演化反应 (OER) 催化. 化MOF表现出卓越的性能,减少过度电位并提高质量活性,以实现高效的OER催化.
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
- 催化剂是一种催化剂.
背景情况:
- 金属有机框架 (MOF) 是氧化演化反应 (OER) 的有希望的催化剂.
- 调整金属活性中心的协调环境是改善MOF催化性能的关键.
- 将素纳入MOF配体对OER的影响尚未得到充分研究.
研究的目的:
- 调查素替代 (Br,Cl,F) 对OER的FeNi-MOF中铁酸连体的影响.
- 优化MOF的协调微环境,以增强开放资源活动.
- 为了建立一个结构-活性关系之间的联体电负性和催化性能.
主要方法:
- 一系列X-FeNi-MOFs (X = Br,Cl,F) 与不同化铁酸连接物的合成.
- 密度函数理论 (DFT) 计算分析电子结构变化和反应机制.
- 电化学测试以评估OER活动,包括超电位和质量活动测量.
主要成果:
- 理论计算表明,增加的素电子阴性 (F > Cl > Br) 增强了Ni原子电荷,并将Ni-3d和O-2p波段更接近费米水平.
- 这种电子调制促进含氧中间体的吸附,并降低了OER激活屏障.
- F-FeNi-MOFs表现出最高的OER活性,在10 mA cm-2.2时达到218 mV的超低超电位.
- 与非功能化MOF相比,质量活动增强了7倍.
结论:
- 在FeNi-MOF中对铁酸连体的素功能化是一种有效的策略,可以调节电子结构并提高OER性能.
- 的结合在OER活动中产生了最显著的改善,突出显示了电子阴性素的潜力.
- 这项研究为设计高性能MOF催化剂的设计提供了一条新的途径,通过连接体工程来实现氧气演化反应.
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