Radiation Chemistry in Environmental Transmission Electron Microscopy

Environmental transmission electron microscopy (E-TEM) enables direct observation of nanoscale chemical processes crucial for catalysis and materials design. However, the high-energy electron probe can dramatically alter reaction pathways through radiolysis, the dissociation of molecules under electron beam irradiation. While extensively studied in liquid-cell TEM, the impact of radiolysis in gas phase reactions remains unexplored. Here, we present a numerical model elucidating radiation chemistry in both gas and liquid E-TEM environments. Our findings reveal that while gas phase E-TEM generates radiolytic species with lower reactivity than liquid phase systems, these species can accumulate to reaction-altering concentrations, particularly at elevated pressures. We validate our model through two case studies: the radiation-promoted oxidation of aluminum nanocubes and disproportionation of carbon monoxide. In both cases, increasing the electron beam dose rate directly accelerates their reaction kinetics, as demonstrated by enhanced AlO growth and carbon deposition. Based on these insights, we establish practical guidelines for controlling radiolysis in closed-cell nanoreactors. This work not only resolves a fundamental challenge in electron microscopy but also advances our ability to rationally design materials with sub-Ångstrom resolution.