Modulating the Electronic Structures of Dual-Atom Catalysts via Coordination Environment Engineering for Boosting CO₂...

Dual-atom catalysts (DACs) have emerged as efficient electrocatalysts for CO₂ reduction owing to the synergistic effect between the binary metal sites. However, rationally modulating the electronic structure of DACs to optimize the catalytic performance remains a great challenge. Herein, we report the electronic structure modulation of three Ni₂ DACs (namely, Ni₂ -N₇ , Ni₂ -N₅ C₂ and Ni₂ -N₃ C₄ ) by the regulation of the coordination environments around the dual-atom Ni₂ centres. As a result, Ni₂ -N₃ C₄ exhibits significantly improved electrocatalytic activity for CO₂ reduction, not only better than the corresponding single-atom Ni catalyst (Ni-N₂ C₂ ), but also higher than Ni₂ -N₇ and Ni₂ -N₅ C₂ DACs. Density functional theory (DFT) calculations revealed that the high electrocatalytic activity of Ni₂ -N₃ C₄ for CO₂ reduction could be attributed to the electronic structure modulation to the Ni centre and the resulted proper binding energies to COOH* and CO* intermediates.