Designing Single Superatom Catalysts for Suzuki Reaction

Analogous to single atom catalysts (SACs), two intriguing "single superatom catalysts" (SSCs), namely isomers <b>A</b> and <b>B</b> of C₅₈ZrO, were designed by replacing two neighboring carbon atoms of C₆₀ with the ZrO superatom with an electronic structure similar to that of Pd. Our results demonstrate that isomer <b>A</b> of C₅₈ZrO possesses better catalytic activity with a smaller rate-limiting energy barrier of 23.8 kcal/mol for the Suzuki reaction than isomer <b>B</b> with 37.1 kcal/mol. In particular, all of the C_<i>n</i>-2ZrO (<i>n</i> = 50, 60, 70, and 80) nanoclusters with the same ZrO-substituent mode as isomer <b>A</b> exhibit a catalytic performance comparable to that of 22.7 kcal/mol for the commonly used catalyst Pd(PPh₃)₂, indicating that this proposed strategy works for various fullerenes of different sizes. Moreover, it is found that cationic C₅₈ZrO exhibits better catalytic activity than the corresponding neutral and anionic C₅₈ZrO. Hence, the electrophilic Br atom and BF₄ superhalogen were respectively embedded into the inner cavity of C₅₈ZrO to induce positive charge on the outer shell, which successfully realized the enhanced catalytic performance of the resulting (super)halogen@C₅₈ZrO catalysts with rate-limiting energy barriers of 17.4 and 21.5 kcal/mol, respectively. This study provides valuable theoretical insights into how superatoms can serve as outstanding alternatives to traditional atoms and as building blocks for novel catalysts.