Chemical Structure and Distribution in Nickel–Nitrogen–Carbon Catalysts for CO2 Electroreduction Identified by Scanning Transmission X‑ray Microscopy

Atomically dispersed metal-nitrogen-carbon (M-N-C) materials are a class of electrocatalysts for fuel cell and electrochemical CO₂ reduction (CO₂R) applications. However, it is challenging to characterize the identity and concentration of catalytically active species owing to the structural heterogeneity of M-N-C materials. We utilize scanning transmission X-ray microscopy (STXM) as a correlative spectromicroscopy approach for spatially resolved imaging, identification, and quantification of structures and chemical species in mesoscale regions of nickel-nitrogen-carbon (Ni-N-C) catalysts, thereby elucidating the relationship between Ni content/speciation and CO₂R activity/selectivity. STXM results are correlated with conventional characterization approaches relying on either bulk average (X-ray absorption spectroscopy) or spatially localized (scanning transmission electron microscopy with electron energy loss spectroscopy) measurements. This comparison illustrates the advantages of soft X-ray STXM to provide spatially resolved identification and quantification of active structures in Ni-N-C catalysts. The active site structures in these catalysts are identified to be atomically dispersed NiN _x /C sites distributed throughout entire catalyst particles. The NiN _x /C sites were notably demonstrated by spectroscopy to possess a variety of chemical structures with a spectroscopic signature that most closely resembles nickel(II) tetraphenylporphyrin molecules. The quantification and spatial distribution mapping of atomically dispersed Ni active sites achieved by STXM address a target that was elusive to the scientific community despite its importance in guiding advanced material designs.