Catalytic activity, thermal stability and structural evolution of PdCu single-atom alloy catalysts: the effects of size and morphology

Single-atom alloys (SAAs) have been emerging as an important field of research in electrocatalysis owing to extremely high atom utilization, unique structure and high catalytic activity. In this work, the catalytic properties and thermal stability of PdCu SAAs with a crown-jewel (CJ) structure are studied by density functional theory (DFT) calculations and the molecular dynamics (MD) simulation method. The DFT results reveal that CJ-structured PdCu SAAs show excellent HER and ORR catalytic performance, and can be regarded as a promising alternative to Pt catalysts towards the ORR or HER. Additionally, we attempt to explain the high catalytic activity of PdCu SAAs by electronic structure analysis. In addition, MD simulation results confirm the thermal stability of CJ-structured PdCu. More importantly, we found that CJ-structured PdCu clusters undergo a structural transformation from cuboctahedral (Cubo) to icosahedral (Ico) structure by heating or after the adsorption of reaction intermediate, which indicates that Cubo is less stable than the Ico structure. Besides, Cubo–Ico transformation is size-dependent and only found in small clusters. Furthermore, the effects of size and morphology on melting properties are discussed. The melting point increases as cluster size increases, which agrees well with Pawlow's law.