Constructing of Ni-Nx Active Sites in Self-Supported Ni Single-Atom Catalysts for Efficient Reduction of CO₂ to CO

The electrochemical carbon dioxide reduction reaction (CO₂RR) represents a promising approach for achieving CO₂ resource utilization. Carbon-based materials featuring single-atom transition metal-nitrogen coordination (M-N_x) have attracted considerable research attention due to their ability to maximize catalytic efficiency while minimizing metal atom usage. However, conventional synthesis methods often encounter challenges with metal particle agglomeration. In this study, we developed a Ni-doped polyvinylidene fluoride (PVDF) fiber membrane via electrospinning, subsequently transformed into a nitrogen-doped three-dimensional self-supporting single-atom Ni catalyst (Ni-N-CF) through controlled carbonization. PVDF was partially defluorinated and crosslinked, and the single carbon chain is changed into a reticulated structure, which ensured that the structure did not collapse during carbonization and effectively solved the problem of runaway M-Nx composite in the high-temperature pyrolysis process. Grounded in X-ray photoelectron spectroscopy (XPS) and X-ray absorption fine structure (XAFS), nitrogen coordinates with nickel atoms to form a Ni-N structure, which keeps nickel in a low oxidation state, thereby facilitating CO₂RR. When applied to CO₂RR, the Ni-N-CF catalyst demonstrated exceptional CO selectivity with a Faradaic efficiency (FE) of 92%. The unique self-supporting architecture effectively addressed traditional electrode instability issues caused by catalyst detachment. These results indicate that by tuning the local coordination structure of atomically dispersed Ni, the original inert reaction sites can be activated into efficient catalytic centers. This work can provide a new strategy for designing high-performance single-atom catalysts and structurally stable electrodes.