选择性整合分子催化单元到基于双二烯的共价有机框架,用于特定的光催化燃料生产
Dengmeng Song1, Wenhua Xu1, Wei He1
1Key Laboratory of Synthetic and Natural Functional Molecule of the Ministry of Education, College of Chemistry & Materials Science, Northwest University, Xi'an 710069, China.
Inorganic chemistry
|February 8, 2024
概括
这项研究将分子催化剂集成到共价有机框架中,以增强光催化进化和二氧化碳减排. 功能化框架显示,这两种反应的催化活性和选择性显著提高.
科学领域:
- 材料科学 材料科学 材料科学
- 催化剂是一种催化剂.
- 摄影化学的使用
背景情况:
- 分子金属化合物显示出进化 (HER) 和二氧化碳减排 (CO2RR) 的前景.
- 分子催化剂的异质化改善了它们的实际应用.
- 共价有机框架 (COF) 为催化剂固定提供可调节的平台.
研究的目的:
- 在COF上在现场构建分子催化单位,用于光催化HER和CO2RR.
- 为了提高HER和CO2RR的催化性能和选择性.
- 为了研究从光敏剂到催化场所的电子转移机制.
主要方法:
- 在COF的双胺位点上进行[Cp*Ir(Bpy) Cl]+和[Ru(Bpy) ((CO) 2Cl2]的现场构造.
- 在可见光下的光催化演化反应 (HER).
- 光催化二氧化碳还原反应 (CO2RR) 形成.
- 光发光谱学和理论计算来研究电子转移.
主要成果:
- TpBpy-Ir实现了H2生产率为760μmol g-1 h-1,是未经修改的COF的6.7倍.
- TpBpy-Ru显示HCOOH生产率为271μmol g-1 h-1 ,具有88%的选择性.
- 对照实验证实了催化增强是由于内置的分子单元.
- 从[Ru(Bpy) ]Cl2光敏感剂到催化剂部位的电子转移得到证实.
结论:
- 在COF上分子催化剂的异质化是有效的光催化剂的有效策略.
- 开发的TpBpy-M材料表现出对HER和CO2RR的优越活性和选择性.
- 该研究阐明了用于催化还原的光诱导电子转移的机制.
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