Department of Chemistry and Biochemistry, University of California, Los Angeles, Los Angeles, California 90095-1569, United States.
California NanoSystems Institute, Los Angeles, California 90095, United States.
J Phys Chem Lett. 2022 May 19;13(19):4321-4334. doi: 10.1021/acs.jpclett.2c00628. Epub 2022 May 10.
Improvements in spectroscopy have enabled the catalysis community to investigate the dynamic nature of catalysts under operating conditions with increasing detail. Still, the highly dynamic nature of some catalysts, such as fluxional supported subnano clusters, presents a formidable challenge even for the most state-of-the-art techniques. The reason is that such fluxional catalytic interfaces contain a variety of thermally accessible states. spectroscopies used in catalysis generally fall into two categories: ensemble-based techniques, which provide spectra containing the signals of the entire ensemble of states of the catalyst and are not necessarily dominated by the most active species, and localized techniques, which provide atomistic-level information about the dynamics of active sites in a very small area, which might not include the most active species. Combining many different kinds of techniques can provide detailed insight; however, we propose that effective utilization of specific computational techniques and approaches within the fluxionality paradigm can fill the gap and enable atomistic characterization of the most relevant catalytic sites.
光谱学的进步使催化界能够更详细地研究催化剂在操作条件下的动态特性。然而，一些催化剂的高度动态性质，例如流体支撑的亚纳米簇，即使是最先进的技术也构成了巨大的挑战。原因是这种流体催化界面包含多种热可及状态。催化中使用的光谱学一般分为两类：基于整体的技术，提供包含催化剂所有状态信号的光谱，不一定由最活跃的物种主导，以及局域技术，提供关于非常小区域中活性位点动态的原子级信息，这些信息可能不包括最活跃的物种。结合许多不同种类的技术可以提供详细的见解；然而，我们提出，在流变性范例中有效利用特定的计算技术和方法可以填补空白，并实现最相关催化位点的原子级表征。
