Predicting the Structure of MoS₃ and Designing Transition-Metal-Doped Catalysts for Efficient CO₂ Electroreduction

The development of efficient and highly selective catalysts for the electrochemical CO₂ reduction reaction (CO₂RR) is crucial for achieving carbon neutrality and sustainable energy cycles. In this study, the stable structure of the MoS₃ monolayer was determined using the crystal structure prediction software CBD-GM. Owing to its distinct sulfur coordination environments and large dipole moment, MoS₃ serves as an ideal support for single-atom catalysts. By doping transition metals at specific sulfur sites (S₁-S₃), we systematically screened a series of single-atom configurations for CO₂ activation. The results demonstrate that CO₂ molecules are effectively activated when Sc, Mn, Fe, Co, and Ni single atoms are doped at the S₂ site. Remarkably, Co_S2@MoS₃ and Ni_S2@MoS₃ are demonstrated as highly effective catalysts for selective CO₂-to-CH₄ conversion, with low limiting potentials of -0.17 and -0.49 V, respectively. This study provides theoretical insights into the rational design of MoS₃-based single-atom systems for efficient and selective CO₂ electroreduction.