Electronegativity-Driven Frontier Orbital Engineering in B-Ti Diatomic Synergy Enables Selective Li2C2O4 Conversion in Li-CO2 Batteries AITranslate

Basic Information:

DOI：

Chinese Library Classification Number:

Citation Information:

s a promising alternative to sluggish Li2CO3-based Li-CO2 electrochemistry, Li2C2O4 offers a favorable 2e− discharge pathway, yet its selective formation and reversible decomposition remain debated. Herein, we propose a nonmetal-metal synergistic catalyst—B-Ti coregulated layered transition metal boride Ti18B18O9/graphene (B-Ti/TiBOG)—to enable efficient CO2-to-Li2C2O4 conversion via frontier orbital engineering (FOE). Density functional theory (DFT) and ab initio molecular dynamics (AIMD) simulations reveal that the low electronegativity of B (O > N > C > B) induces asymmetric Ti coordination, driving strong B 2p and Ti 3d orbital hybridization near the Fermi level, and better structural stability, outperforming C/N/O-Ti analogs. Interestingly, this unique FO alignment activates CO2 by populating its antibonding orbitals through a bidirectional “acceptance-feedback” mechanism to enhance CO2 adsorption (from −0.19 to −1.05 eV). The B-Ti synergy selectively stabilizes Li2C2O4 nucleation while kinetically suppressing its conversion to Li2CO3 (barrier > 0.68 eV). Consequently, the hybrid B-Ti/TiBOG catalyst achieves exceptional bifunctionality, yielding a minimal total overpotential (0.75 V) for CO2-to-Li2C2O4 cycling—maintained in the tetraethylene glycol dimethyl ether (TEGDME) solvent environments. This work highlights electronegativity-driven FOE in B-Ti diatomic synergy as key for rechargeable Li-CO2 batteries.