Coalescence and shape oscillation of Au nanoparticles in CO hydrogenation to methanol.

Recently, there has been renewed interest in Au nanoparticle (Au NP) catalysts owing to their high selectivity for CO hydrogenation to methanol. However, there is still limited knowledge on the main factors of the catalytic activity and product selectivity of Au NPs. To address this issue, we utilized transmission electron microscopy to observe the evolution of Au NP catalysts during CO hydrogenation to methanol at 260 °C under ambient pressure. During the reaction, Au NPs sized ≤5 nm coalesced rapidly, forming stable Au NPs sized 5-10 nm with oscillating shapes. The first-principles calculations demonstrated that the adsorption of the reactant gas CO is the main factor in inducing the coalescence of Au NPs, and CO and/or HO adsorption generated by the reaction caused the oscillation of the Au NP shape. Furthermore, the adsorption of various gas molecules resulted in continuous changes in the structure of the catalyst active center. In this study, the observation of the dynamic evolution of the Au NP morphology is important in understanding the structural transformation of Au NP catalysts at the nanometer scale and determining the active site motifs under the reaction conditions. Moreover, this would allow us to further understand the size effect and the dynamic evolution behavior of the active center of Au NP catalysts, thereby providing a new idea for the development and application of new catalysts and strong theoretical support for heterogeneous catalytic reaction mechanisms.