金属有机框架用于光催化
Xin-Ping Wu1, Laura Gagliardi1, Donald G Truhlar1
1Department of Chemistry, Chemical Theory Center, and Minnesota Supercomputing Institute , University of Minnesota , Minneapolis , Minnesota 55455-0431 , United States.
Journal of the American Chemical Society
|May 30, 2018
概括
将 (Ce) 纳入金属有机框架 (MOF) 便于连接物到金属的电荷转移 (LMCT),增强光生成的电荷分离. 功能化连接器进一步调整电子结构,用于光催化水分裂等应用.
科学领域:
- 材料科学
- 摄影化学
- 无机化学
背景情况:
- 体到金属的电荷转移 (LMCT) 对于材料中的光生成电荷的分离至关重要.
- 金属有机框架 (MOF) 为各种应用提供可调节的结构.
研究的目的:
- 研究不同金属节点 (M = Zr,Hf,Th,Ti,U,Ce) 的UiO-66MOF电子结构.
- 确定LMCT在这些MOF中的可行性,并确定促进它的战略.
- 探索 (Ce) 基MOF在光催化应用中的潜力,例如水分解.
主要方法:
- 对各种MOF进行了计算电子结构计算.
- 分析了具有M6O4 ((OH)) 4无机节点的MOF的电子结构.
- 研究了链接器功能化对LMCT能量的影响.
主要成果:
- 仅在 (Ce) 基MOF中发现LMCT具有有利作用.
- 在这些结构中,低空的Ce4+4f轨道促进LMCT.
- 使用电子捐赠或提取组的连接器功能允许调整LMCT能量.
- 增加连接器上的功能组增加了LMCT能量调节.
结论:
- 将Ce4+纳入MOF节点是一个有效的策略来促进LMCT.
- Ce-MOF可以通过链接器功能化来设计用于水分裂等特定反应.
- 这些发现支持Ce-MOF在可见光驱动光催化中的应用.
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