摘要： Conversion of CO2 gas to CO fuels is one of the most promising solutions for the increasing threat of global warming and energy crisis. The efficient catalyst Ni–Au dumbbell converting CO2 into CO at elevated temperatures has high CO product selectivity; however, the accompanied atomic diffusion and subsequent surface reconstruction affect the catalytic efficiency of chemical reaction. Atomic scale characterization of structural evolution of the catalyst, which is essential to correlate the functional mechanism to active catalyst surfaces, is yet to be studied. Here, in situ transmission electron microscopy experiments and atomistic simulations are performed to characterize the structural evolution of Ni–Au dumbbell nanoparticles under two different external stimuli. In the condition of high temperature and vacuum, the Ni–Au nanostructure reveals a clear shape reconstruction from the initial dumbbell to core–shell-like, which is induced by capillary force to minimize free surface energy of the system. The shape transformation involves two stages of processes, initial fast Au diffusion followed by slow source-controlled diffusion. At ambient temperature, the combination of CO2 and electron flux surprisingly induces analogous structural transformation of Ni–Au nanostructure, where the associated chemical reaction and CO absorption stimulate the Au migration on Ni surface. Such surface reconstruction can be widely present in catalytic reactions in different environmental conditions, and the results herein demonstrate the detailed processes of Ni–Au structure evolution, which provide important insights for understanding the catalyst performance.