Integrative Ni ₁ –P <i> _x </i> Catalytic Pairs for Low‐Concentration CO ₂ Electroreduction

Abstract The electrochemical CO 2 reduction reaction (CO 2 RR) powered by renewable electricity offers a promising approach for sustainable carbon utilization. However, under industrially relevant low CO 2 concentrations (5–15 vol.%), the efficiency and selectivity of electrochemical CO 2 RR are significantly constrained by the limited CO 2 supply and the competitive hydrogen evolution reaction (HER). Herein, we report integrative Ni 1 –P x catalytic pairs (Ni 1 –P x /ICPs) that exhibit super CO 2 ‐to‐CO conversion efficiency under low‐concentration CO 2 conditions. In situ attenuated total reflectance surface‐enhanced infrared absorption spectroscopy (ATR‐SEIRAS) and X‐ray absorption spectroscopy (XAS) measurements show that P incorporation modulates the electrochemical microenvironment and accelerates reaction kinetics. H/D isotopic substitution experiments and theoretical calculations unveil a mechanistic transition from an Eley–Rideal to Langmuir–Hinshelwood pathway, enabled by cooperative adsorption on adjacent Ni and P sites. Notably, a hydrogen‐bonded six‐membered Ni–C–O–H–O–P–Ni ring forms between adsorbed CO 2 and H 2 O, facilitating proton‐coupled electron transfer and lowering the reaction barrier. This unique adsorption motif enhances CO 2 activation, suppresses HER, and enables efficient CO generation at low CO 2 concentrations. Our findings show the importance of atomically dispersed catalytic pairs for advancing carbon utilization and overcoming selectivity challenges in electrochemical hydrogenation.