Design of High-Performance Pd-Based Alloy Nanocatalysts for Direct Synthesis of H₂O₂

The direct synthesis of hydrogen peroxide (H 2 O 2 ) is a promising alternative to the commercialized indirect process. However, it is still a big challenge for the development of Pd-based catalysts with outstanding activity and selectivity, because the design and optimization of the efficient catalysts cannot be effectively achieved solely on the basis of the well-known Sabatier analysis. In this paper, we proposed a strategy to design more efficient Pd-based nanocatalysts combining density functional theory (DFT) calculations and Sabatier analysis. The average valence electron of Pd-shell atoms is identified as the intrinsic factor for the activity and selectivity of the Pd-based nanocatalysts, which can be effectively tuned by the dopants. By introducing dopants with suitable electronegativity, the valence electrons of Pd-shell atoms could be adjusted to the optimal range to enhance the activity and selectivity of the nanocluster simultaneously. With this strategy, Pd-W, Pd-Pb, Au-Pd-W, Au-Pd-Pb, Au-Pd-Mo, and Au-Pd-Ru are predicted as the potential candidates with catalytic performance far exceeding the state of the art experimental systems by a scan of the periodic table. This work not only predicts potential Pd-based alloy nanocatalysts for direct synthesis of H 2 O 2 for future experiments but also provides a viable way for the design of highly efficient heterogeneous catalysts in extensive applications.