Asymmetric charge polarized heteronuclear nonmetal dual-atom catalysts for efficient electrocatalytic carbon dioxide...

Electrocatalytic carbon dioxide (CO₂) reduction reaction (CO₂RR) is a crucial pathway for achieving carbon neutrality and facilitating the circular utilization of carbon resources. Using first principles study, we designed a series of single-atom catalysts (SACs) and dual-atom catalysts (DACs) anchored at S vacancies in monolayer molybdenum disulfide (MoS₂), with boron (B) and carbon (C) functioning as active sites. Our results reveal that exclusively parallel configured DACs (BB-, BC- and CC-MoS₂) demonstrate sufficient CO₂ capture and activation capabilities. Comprehensive characterization via binding energy (E_b) analysis, ab initio molecular dynamics (AIMD) simulations, partial density of states (PDOS) calculations and work function (Φ) evaluation confirms these catalysts possess exceptional stability, enhanced electrical conductivity, and superior electron transfer capabilities. Charge density difference analysis combined with Bader charge analysis elucidates that asymmetric charge distribution, induced by electrostatic polarization and charge transfer at exposed active sites, is a critical prerequisite for achieving high catalytic performance. This electronic configuration enables BC-MoS₂ to achieve selective conversion of CO₂ to methane (CH₄) at a low limiting potential (U_L = -0.48 V), outperforming both BB- and CC-MoS₂. This work provides valuable insights into designing novel and efficient MoS₂-based electrocatalysts.