Stone Ilana B, Starr Rachel L, Hoffmann Norah, Wang Xiao, Evans Austin M, Nuckolls Colin, Lambert Tristan H, Steigerwald Michael L, Berkelbach Timothy C, Roy Xavier, Venkataraman Latha
Department of Chemistry, Columbia University New York New York 10027 USA
Center for Computational Quantum Physics, Flatiron Institute New York New York 10010 USA.
Chem Sci. 2022 Sep 1;13(36):10798-10805. doi: 10.1039/d2sc03780g. eCollection 2022 Sep 21.
The electric fields created at solid-liquid interfaces are important in heterogeneous catalysis. Here we describe the Ullmann coupling of aryl iodides on rough gold surfaces, which we monitor using the scanning tunneling microscope-based break junction (STM-BJ) and using mass spectrometry and fluorescence spectroscopy. We find that this Ullmann coupling reaction occurs only on rough gold surfaces in polar solvents, the latter of which implicates interfacial electric fields. These experimental observations are supported by density functional theory calculations that elucidate the roles of surface roughness and local electric fields on the reaction. More broadly, this touchstone study offers a facile method to access and probe in real time an increasingly prominent yet incompletely understood mode of catalysis.
在多相催化中，固液界面处产生的电场至关重要。在此，我们描述了芳基碘化物在粗糙金表面上的乌尔曼偶联反应，我们使用基于扫描隧道显微镜的断结技术（STM - BJ）以及质谱和荧光光谱对其进行监测。我们发现，这种乌尔曼偶联反应仅在极性溶剂中的粗糙金表面上发生，后者暗示了界面电场的作用。这些实验观察结果得到了密度泛函理论计算的支持，该计算阐明了表面粗糙度和局部电场在反应中的作用。更广泛地说，这项具有里程碑意义的研究提供了一种简便的方法，可实时获取并探究一种日益突出但尚未完全理解的催化模式。
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