How In Situ/Operando SERS Illuminates the Environment‐Interface‐Material Nexus in Heterogeneous Catalysis

The development of green and sustainable heterogeneous catalytic reactions represents a crucial pathway to addressing growing global challenges such as energy shortages, environmental pollution, and public health issues. Understanding the coupled mechanisms of “environment‐interface‐material” in heterogeneous catalysis at the molecular level is essential for designing catalysts with high activity, desirable selectivity, and long‐term stability. Surface‐enhanced Raman scattering (SERS) spectroscopy, known for its high sensitivity, surface specificity, minimal water interference, and excellent spectral selectivity, has emerged as a powerful tool for investigating surface and interfacial catalytic processes. This review summarizes recent advances in the application of in situ/operando SERS spectroscopy for monitoring the entire catalytic process, including the evolution of catalyst structures under reaction conditions, real‐time tracking of reactants, intermediates, products, and kinetic analysis via their fingerprint vibrational signals, and the influence of the interfacial micro‐environment on reaction pathways.