Integrative Ni <sub>1</sub> –P <i> <sub>x</sub> </i> Catalytic Pairs for Low‐Concentration CO <sub>2</sub> Electroreduction
Xiuwen Shi, Xiongyi Liang, Lingyue Liu, Fangxin Hu, Yuhang Liu, Yuhang Jin, Yu Yang, Tingting Zhao, Pingping Wang, Jie Ding, Xiao Cheng Zeng, Bin Liu, Hongbin Yang
Abstract
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.