Bimetallic Transition Metal@Au Core–Shell Nanocatalysts for Enhanced Heterogeneous Fenton-Like Reactions: A Theoretical Study

Gold-based core–shell catalysts for Fenton-like reactions have attracted significant attention in chemodynamic therapy. Nevertheless, their rational design remains challenging due to poorly understood structure–performance relationships. Combining density functional theory with machine learning, this work established a general design principle for bimetallic core–shell nanoparticles with a superior H 2 O 2 dissociation performance. Incorporating a secondary transition metal as the core can optimize the electronic distribution of the Au shell, modulate adsorption strength of reaction intermediates, and thereby enhance catalytic performance. The catalytic activity for H 2 O 2 dissociation on M@Au (M denotes Mn, Ni, Cu, Mo, Ru, Rh, Pd, Ag, Re, Ir, and Pt) core–shell clusters exhibits a volcano-shaped relationship with the adsorption strength. Benefiting from synergistic bimetallic effects, Ru@Au, Os@Au, and Cu@Au exhibit significantly enhanced performance compared to the pristine Au counterpart. Furthermore, one energetic and two structural descriptors were constructed, which quantitatively link inherent catalyst properties to catalytic performance. This work can offer a fundamental framework for advancing Fenton-like catalysts.