Direct electrochemical functionalization of methane remains fundamentally limited by the difficulty of stabilizing reactive CH_x intermediates while suppressing overoxidation and competing side reactions. Using grand-canonical ensemble density functional theory (GCE-DFT), we reveal how an applied anodic potential induces evolution of the axial coordination environment on a graphene-supported IrN₄ single-atom catalyst to enable selective methane amination. Constant-potential GCE-DFT calculations show that IrN₄ evolves into a bis-axial *CH₂–*NH₂ resting state that dominates over a broad potential–pH window. This potential-induced configuration offers dual advantages: It excludes oxygenated ligands to suppress the oxygen evolution reaction and stabilizes a reactive, electrophilic surface *CH₂ carbene. Electronic structure analyses identify minimized Pauli repulsion and cooperative σ–π interactions as the key factors governing this preferential axial coordination. Kinetic analyses further demonstrate that *CH₂ in this bis-axial *CH₂–*NH₂ motif acts as a chemoselective electrophile that delivers low-barrier, concerted C–N coupling with solution-phase NH₃, outperforming competing C–C and C–O coupling pathways. These findings establish potential-induced axial coordination as a powerful design principle for directing single-atom catalysis and provide a mechanistic foundation for selective methane-to-amine conversion.

For electrocatalytic reduction of CO₂ to CO, the stabilization of intermediate COOH^* and the desorption of CO^* are two key steps. Pd can easily stabilize COOH^*, whereas the strong CO^* binding to Pd surface results in severe poisoning, thus lowering catalytic activity and stability for CO₂ reduction. On Ag surface, CO^* desorbs readily, while COOH^* requires a relatively high formation energy, leading to a high overpotential. In light of the above issues, we successfully designed the PdAg bimetallic catalyst to circumvent the drawbacks of sole Pd and Ag. The PdAg catalyst with Ag-terminated surface not only shows a much lower overpotential (-0.55 V with CO current density of 1 mA/cm²) than Ag (-0.76 V), but also delivers a CO/H₂ ratio 18 times as high as that for Pd at the potential of -0.75 V vs. RHE. The issue of CO poisoning is significantly alleviated on Ag-terminated PdAg surface, with the stability well retained after 4 h electrolysis at -0.75 V vs. RHE. Density functional theory (DFT) calculations reveal that the Ag-terminated PdAg surface features a lowered formation energy for COOH^* and weakened adsorption for CO^*, which both contribute to the enhanced performance for CO₂ reduction.