First principles insights into the relative stability, electronic and catalytic properties of core–shell, Janus and mixed structural patterns for bimetallic Pd–X nano-alloys (X = Co, Ni, Cu, Rh, Ag, Ir, Pt, Au)

The three well-known orderings of the two constituting atomic species in a bimetallic nano-alloy - core-shell, Janus and mixed structural patterns - may be interconvertible depending on the synthesis conditions. Using first principles electronic structure calculations in the present work, we look for the microscopic origin for such structural transformation considering eight Pd-related bimetallic nano-alloys. Our analysis shows that it is the change in atom-atom covalency that is responsible for such structural transformation. Our study also reveals that the three patterns are distinctly identified in terms of total orbital hybridization. Finally, we have analyzed the trend in the relative catalytic activity for the three structures of each bimetallic nano-alloy using the d-band model. Our analysis indicates that the trend in the catalytic activity for the bimetallic Pd-X nano-alloys seems to be intermediate to those of the pristine Pd and Pt nano-clusters possessing similar structure and equal number of total atoms. Among the studied binary nano-alloys, the bimetallic Pd-Ni nano-alloy appears as the most suitable binary pair to develop a non-Pt catalyst.