Application of Scanning Transmission Electron Microscopy in the Studies of Atomically Dispersed Catalysts
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摘要: 球差校正扫描透射电子显微镜（STEM）因其原子级的空间分辨率和元素解析能力，在纳米功能材料的结构和成分分析中得到广泛使用。扫描透射电子显微镜高角环形暗场像技术（STEM-HAADF）凭借独特的原子序数衬度（Z衬度）和电子通道效应，在负载型纳米催化剂的结构研究中有着显著优势。通过STEM-HAADF成像，研究人员不仅可以直接观测到单个贵金属原子在较轻的载体上的实空间分布，还可以实现对载体表面上不同的负载贵金属物种的统计分析，这为近十年兴起的单原子催化剂研究提供了最重要的结构分析支持。相对于STEM-HAADF成像，基于STEM的X射线能谱（EDS）和电子能量损失谱（EELS）的谱学分析技术则能够在纳米尺度乃至原子尺度提供直接的化学成分或化学价态信息。成像和谱学的结合能够更准确地确定负载的金属原子在基底上的空间构型。进一步将原位电镜技术引入扫描透射电子显微镜内，则可以在时间尺度上探究催化剂在接近工作环境下的结构演化，从而更全面地揭示催化剂化学活性的结构起源与失效机制。本文结合近几年的部分代表性研究成果，简要介绍球差校正STEM技术在原子级分散负载催化剂研究中的应用，并对其在该研究领域的进一步发展进行了展望。Abstract: Aberration-corrected scanning transmission electron microscopy(STEM) has been widely used in the structural and compositional analysis of functional materials due to its atomic-level spatial resolution in imaging and spectroscopic analysis.In particular, STEM high-angle annular dark-field(STEM-HAADF) imaging has significant advantages in the structural analysis of supported metal catalysts by virtue of its atomic-number contrast(Z contrast) and electron channeling effect.Through STEM-HAADF imaging, the distribution of heavy noble metal atoms on light support materials can be directly visualized in real space with single-atom sensitivity, and statistical analysis of different surface species can also be obtained, which makes STEM-HAADF imaging the most important structural analysis technique for the studies of emerging single-atom catalysts(SACs).As complementary techniques to STEM-HAADF imaging, STEM-based X-ray energy dispersive spectroscopy(EDS) and electron energy loss spectroscopy(EELS) can directly probe chemical composition and/or valence states at the nanoscale or even the atomic scale.The combination of imaging and spectroscopy in STEM thus provides a comprehensive analysis of the catalyst structure from multiple perspectives.Furthermore, when combined with in-situ electron microscopy techniques, the structural evolution of the catalyst under simulated working environments can be explored on the temporal axis, helping to unveil the structural origins of the catalytic activity and the failure mechanism of the catalysts.This review article briefly introduces the application of aberration-corrected STEM in the research of atomically dispersed supported catalysts, and provides prospects for the future development of STEM techniques for catalysis research.
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