Preparation of new titanium nitride-carbon nanocomposites in supercritical benzene and their oxygen reduction activity in alkaline medium

Highlights: • TiN/C/graphene composite (SIV) was synthesized using supercritical benzene medium. • SIV catalyst shows high ORR activity due to both TiN and graphene phases. • SIV improves ORR via a mainly 4-electron pathway to form water and around 16% H₂O₂. • SIV exhibits high stability due to reduce H₂O₂ and prevent surface poisoning. - Abstract: Titanium nitride-carbon nanocomposites are synthesized by the reaction of TiCl₄ and NaN₃ in supercritical benzene medium that also serves as a carbon source. The as-prepared precursors (SI, SII) are subjected to several heat treatments (SIII–SV). The synthesized nanoparticles are characterized by X-ray photoelectron spectroscopy (XPS), Fourier transform infrared spectroscopy (FTIR), X-ray diffraction (XRD), field emission scanning electron microscopy (FE-SEM), and transmission electron microscopy (TEM). The samples are tested as electrocatalyst for oxygen reduction reaction in an alkaline electrolyte. It is shown that the electrocatalytic properties of the synthesized nanoparticles are highly dependent on the heat treatment atmosphere and duration. The heat treatment under ammonia atmosphere at 1000 °C for 10 h (SIV) increased the ORR mass activity from −0.64 (SI) to −1.28 mA mg⁻¹ (SIV) at −0.6 V vs. SCE. Moreover, the heat treated sample (SIV) shows almost twice ORR mass activity as commercial TiN. Rotating disk electrode (RDE) measurements exhibit ORR on commercial TiN proceeds via two parallel pathways including two and four electrons, resulting in almost 60% H₂O₂ production, while SIV sample improves ORR by reducing H₂O₂ formation to almost 16%. The high ORR activity and stability of the sample SIV are mainly due to (i) random layer structure of carbon that combines through a hybrid state with TiN nanoparticles, (ii) unstoichiometric nitrogen and oxygen doped into TiN lattice, and (iii) higher electrochemical surface area. Moreover, the possible pathways of carbon phase formation in vicinity of supercritical reaction are discussed