Titanium-, Nitrogen-Doped Carbon Flowers Catalyze Electrochemical Nitrate Reduction Reaction to Ammonia.

An emerging design heuristic for electrochemical nitrate reduction (NORR) catalysts is synthesizing electron-deficient sites to facilitate binding of electron-rich NO. However, this rule has rarely been applied to metal-, nitrogen-doped carbon (MNC) catalysts. Titanium (Ti), with low electronegativity and high NORR reactivity, is a compelling MNC candidate. To date, atomically dispersed TiN motifs have eluded synthesis due to the strong oxophilicity of Ti. Here, we leverage nitrogen-rich carbon flowers (CF) to overcome synthetic challenges and produce Ti-, N-doped carbon flower (TiCF) catalysts. Advanced materials characterization demonstrates that TiCF catalysts are a mixed phase material with 3/4 of Ti atoms in TiO-like nanoparticles and 1/4 of Ti atoms in novel, atomically dispersed TiN sites. TiCF achieves 61 ± 7% NH-selectivity at -0.70 V vs RHE and 14 ± 5 mA/cm to NH formation (||) at -0.85 V vs RHE in (0.1 M NaOH + 0.1 M NaNO + 0.45 M NaSO) electrolyte. Control studies show both CF morphology and Ti sites are essential for high NORR activity. Density functional theory calculations attribute the NORR reactivity to TiN, which facilitates multiple bond formation with surface intermediates to promote favorable NH synthesis pathways. Thus, TiCF exhibits 60× higher || values than bulk Ti and NH yield rates (>0.06 mmol NH/h/cm) that are competitive with state-of-the-art MNC catalysts (e.g., FeNC, CuNC). TiCF introduces a new class of Ti electrocatalysts, advancing the MNC design space and sustainable NH production.