Formulation and Characterization of 3D-Printable Nitrogen- and Metal-Doped Carbon Inks for ORR Electrode Applications

Additive manufacturing provides a fabrication route for electrode components with controlled macrostructure; however, printable carbon inks that also incorporate oxygen reduction reaction active precursors remain underdeveloped. Here, XC-72 carbon was combined with selected metal precursors to prepare N–C, Fe–N–C, and Pt-containing carbon ink formulations for direct ink writing. The precursor mixtures were incorporated into a polyurethane-based matrix, pyrolyzed at 900 °C, and characterized using X-ray diffraction, oscillatory rheology, rotating ring-disk electrode measurements, Brunauer–Emmett–Teller surface-area analysis, and scanning electron microscopy. XRD confirmed retention of carbon diffraction features and the formation of metal-containing crystalline phases after pyrolysis. Oscillatory rheology showed storage moduli exceeding loss moduli for the tested formulations, indicating elastic-dominant behavior suitable for shape retention during printing. For the PGM-free formulations, incorporation of nitrogen and iron precursors improved ORR onset potential, half-wave potential, limiting current density, and electron-transfer selectivity relative to the carbon control. BET analysis showed a decrease in accessible surface area after precursor incorporation, consistent with partial pore blocking or structural modification during pyrolysis. These results establish a printable formulation platform for ORR-active carbon-based inks, while future work is required to isolate the effects of printed architecture, pore hierarchy, and durability under fuel-cell operating conditions.