Revealing Sintering Kinetics of MoS₂-Supported Metal Nanocatalysts in Atmospheric Gas Environments via Operando Transmission Electron Microscopy

The decoration of two-dimensional (2D) substrates with nanoparticles (NPs) serve as heterostructures for various catalysis applications. Deep understanding of catalyst degradation mechanisms during service conditions is crucial to improve the catalyst durability. Herein, we studied the sintering behavior of Pt and bimetallic Au-core Pt-shell (Au@Pt core–shell) NPs on MoS2 supports at high temperatures under vacuum, nitrogen (N2), hydrogen (H2), and air environments by in situ gas-cell transmission electron microscopy (TEM). The key observations are summarized as effect of environment: while particle migration and coalescence (PMC) was the main mechanism that led to Pt and Au@Pt NPs degradation under vacuum, N2, and H2 environments, the degradation of MoS2 substrate was prominent under exposure to air at high temperatures. Pt NPs were less stable in H2 environment when compared with the Pt NPs under vacuum or N2, due to Pt–H interactions that weakened the adhesion of Pt on MoS2. Effect of NP composition: under H2, the stability of Au@Pt NPs was higher in comparison to Pt NPs. This is because H2 promotes the alloying of Pt–Au, thus reducing the number of Pt at the surface (reducing H2 interactions) and increasing Pt atoms in contact with MoS2. Effect of NP size: The alloying effect promoted by H2 was more pronounced in small size Au@Pt NPs resulting in their higher sintering resistance in comparison to large size Au@Pt NPs and similar size Pt NPs. The present work provides key insights into the parameters affecting the catalyst degradation mechanisms on 2D supports.