Atomically dispersed 3d metal bimetallic dual-atom catalysts and classification of the structural descriptors

Solid atomic catalysts with well-defined and complex structures are believed to effectively bridge homogeneous and heterogeneous catalysis. Nonetheless, the current limited capacity of “precise engineering” in solid atomic catalysts has led to structural heterogeneity and thus unsatisfactory catalytic selectivity. Here, we show that late 3 d metal cations, such as Co 2+ , Ni 2+ , Cu 2+ , and Zn 2+ , can be assembled to afford combinations of “dual atoms” within zeolitic micropores, and this clearly avoids issues like uncontrolled metal aggregation during synthesis. In this work, by the quantitative evaluation of the structural descriptors over a probe superoxide dismutation reaction, we demonstrate the unique synergistic advantage between (i) neighboring bimetallic active motifs, (ii) tertiary structure around the zeolitic support, and (iii) the local coordination environment. The identification and tunability of the structural descriptors shown in this work unravel a reliable approach to the precise engineering of next-generation solid dual-atom catalysts. • Atom-precise synthesis of supported bimetallic dual-atom catalysts • Reliable approach for precise microenvironment engineering in solid catalysts • Discovery of the interplay between the structural descriptors and catalytic properties • Demonstration of synergistic effect with sorafenib for augmented tumor cell apoptosis We aim to present a creative approach to afford dual-atom bimetallic catalysts in a controlled and modular manner. This directly allows the combinations of different late 3 d metals (forming M 1 -M 2 -supported dual atoms) and shows extensive possibility not limited to catalytic applications. Through the unique synergistic advantage between the two metal species and the tertiary structure around the zeolitic support, we demonstrated the feasibility of developing next-generation dual-atom bimetallic catalysts in a controlled manner as well as the identification of the structural descriptors. The manipulation and control of materials and phenomena at atomic and molecular dimensions are achieved by utilizing the fundamental concepts of coordination and solid-state chemistries. The findings presented in this work reveal the precise engineering of supported dual-atom catalysts (such as combinations of 3 d /4 d metals) over support materials not only for biochemical applications but also for more extensive applications. This shall genuinely bring heterogeneous catalysis toward the molecular frontier that addresses the critical challenges in the field.