Stepping Out of Transition Metals: Activating the Dual Atomic Catalyst through Main Group Elements

In recent years, investigations into atomic catalysts has accelerated significantly. Although different atomic catalysts have been developed, the introduction of main group elements is rarely considered. In this work, the possibility of introducing alkaline/alkaline earth metals (AAEM), post‐transition metal (Post‐TM), and metalloids to form stable graphdiyne‐based dual atomic catalysts (GDY‐DAC) is revealed. The main group elements not only act as a promising separator to improve the loading of DACs but also activate the alkyl chains to facilitate the electroactivity of GDY‐DAC. Most importantly, the main group elements in the GDY‐DAC do not affect the electroactivity of transition or lanthanide metals and even enable subtle modulations on the electronic structures. The p band center is a significant descriptor to modulate the electroactivity in oxides while their applications in the atomic catalysts are unclear. With the further evaluations of machine learning, it is found that the involvements of s‐orbitals and p‐orbitals perturb the prediction accuracies of both formation energies and p‐band center, especially for the AAEM. This work supplies insights that are expected to aid progress in designing main group elements‐based atomic catalysts, which opens a new avenue in designing advanced electrocatalysts. The introduction of main group elements in atomic catalysts is not, at the present time, accompanied by in‐depth understanding. In this work, main group elements are introduced as efficient modulators via the s–p–d orbital couplings in graphdiyne‐based dual atomic catalysts (DAC) and both thermodynamic stability and electroactivity are examined. This work further opens up new development directions for future DACs with broad applications.