Understanding oxide reduction is critical for advancing metal production1,2, catalysis3,4 and energy technologies5. Although carbon monoxide (CO) and hydrogen (H2) are widely used reductants, the mechanisms by which they work are often presumed to be similar, both involving lattice oxygen removal6–9. However, because of growing interest in replacing CO with H2 to lower CO2 emissions, distinguishing gas-specific reduction pathways is critical. Yet, capturing these atomic-scale processes under reactive gas and high-temperature conditions remains challenging. Here we use environmental transmission electron microscopy, which is capable of real-time, atomic-resolution imaging of gas–solid redox reactions10–16, to directly visualize the gas-dependent oxide reduction dynamics in NiO. We show that CO drives surface nucleation and the growth of metallic Ni islands, leading to self-limiting surface metallization. Conversely, H2 activates a coupled surface-to-bulk transformation, where protons from dissociated H2 infiltrate the oxide lattice to promote the inward migration of surface-generated oxygen vacancies and enabling bulk metallization. By contrast, oxygen vacancies formed by CO remain confined near the surface, where they rapidly form a metallic Ni layer that inhibits further reduction. These results reveal distinct atomistic pathways for CO and H2 and provide insights that may guide metallurgical processes and catalyst design.
