在氧化催化剂的MIL-127MOF中框架Ni物种的结构和位点演变
Benjamin Yeh1, Saumil Chheda1,2, Steven D Prinslow2
1Department of Chemical Engineering and Materials Science, University of Minnesota-Twin Cities, 421 Washington Avenue SE, Minneapolis, Minnesota 55455, United States.
Journal of the American Chemical Society
|February 1, 2023
概括
一种新型的金属有机框架 (MOF),Ni-MIL-127,作为一种高度稳定的氧化催化剂. 这种MOF产生了缺陷点,有效地转化,而不需要辅助催化剂.
科学领域:
- 材料科学
- 催化剂
- 纳米技术
背景情况:
- 金属有机框架 (MOF) 提供可调节的催化结构.
- 开发高效和稳定的素寡合化催化剂至关重要.
- MOF中的缺陷工程可以提高催化性能.
研究的目的:
- 合成和描述一个混合价值的氧化MOF,Ni-MIL-127.
- 为了研究Ni-MIL-127的催化活性.
- 了解MOF催化中的缺陷作用.
主要方法:
- 合成Ni-MIL-127 MOF.
- 用热处理来制造缺失的连接器缺陷.
- 烯寡合反应
- 温度编程氧化,1H NMR,XAS和现场NO定位用于缺陷量化.
- 密度函数理论 (DFT) 的计算.
主要成果:
- 在没有辅助催化剂的情况下,Ni-MIL-127表现出前所未有的稳定性 (~20小时) 和用于烯寡合化的活性.
- 热处理产生缺失链接器缺陷,产生催化活性位 (约62%的活性).
- 动力学研究显示激活能量为55-67kJmol-1和第一级依赖压力.
结论:
- 有缺陷的Ni-MIL-127MOF作为高效的烯寡合化前催化剂.
- 缺少连接器缺陷对于产生活性位和启动催化是至关重要的.
- MOF缺陷工程为设计先进的油寡合催化剂提供了一个有前途的策略.
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