Lattice Nitrogen Couples Cu δ+ Stabilization With Pathway Control for CO 2 ‐to‐Methanol Electroreduction

ABSTRACT Dynamic catalyst reconstruction is an unavoidable feature of Cu‐catalyzed CO 2 electroreduction, yet for methanol synthesis it creates a fundamental stability–selectivity conflict: the cathodic potentials required for CO 2 reduction simultaneously destroy the partially oxidized Cu sites needed to retain oxygenated intermediates. Here, we show that lattice‐incorporated nitrogen resolves this conflict by regulating both catalyst evolution and reaction‐pathway selection in amorphous CuO. Nitrogen creates a resilient Cu–N/O coordination environment that suppresses excessive Cu reduction and preserves catalytically relevant Cu δ+ sites. The optimized N/a‐CuO catalyst achieves a methanol Faradaic efficiency of 48% in an H‐type cell and a methanol partial current density of 42.8 mA cm −2 in a flow cell, corresponding to 266.3 µmol h −1 cm −2 . Operando spectroscopy reveals enhanced accumulation of bridge‐bound *CO and its subsequent conversion to oxygenated intermediates. Density functional theory further shows that nitrogen‐induced charge redistribution stabilizes Cu δ+ sites and selectively lowers the free energy of the pathway‐diverging *CHOH intermediate through a favorable C–N interaction, promoting C─O bond retention and methanol formation over methane. These findings establish lattice nitrogen as a strategy for coupling dynamic active‐site stabilization with intermediate‐specific pathway control in multielectron electrocatalysis.