Abstract
Heterogeneous catalysis is pivotal to modern chemical industries, and molecular-level insights into catalytic processes are essential for developing highly efficient catalysts and advancing energy conversion technologies. Tip-enhanced Raman spectroscopy (TERS), which integrates scanning probe microscopy with plasmon-enhanced Raman spectroscopy, provides chemical and topographic information simultaneously with exceptional sensitivity and nanoscale spatial resolution. This technique is ideally suited for the nanoscale chemical characterization of solid catalysts, enabling direct structure-performance correlations. In this review, we first introduce the fundamental principles of TERS, and then highlight its key applications in probing heterogeneous catalysis, focusing on critical aspects such as active sites, molecular activation pathways, conversion efficiency, chemical selectivity, and operando studies. We conclude by discussing current challenges and potential strategies to advance TERS in heterogeneous catalysis, and by outlining future directions for the field.