Facile Synthesis and Superior Catalytic Activity of Nano-TiN@N–C for Hydrogen Storage in NaAlH₄

Herein, we synthesize successfully ultrafine TiN nanoparticles (<3 nm in size) embedded in N-doped carbon nanorods (nano-TiN@N-C) by a facile one-step calcination process. The prepared nano-TiN@N-C exhibits superior catalytic activity for hydrogen storage in NaAlH₄. Adding 7 wt % nano-TiN@N-C induces more than 100 °C reduction in the onset dehydrogenation temperature of NaAlH₄. Approximately 4.9 wt % H₂ is rapidly released from the 7 wt % nano-TiN@N-C-containing NaAlH₄ at 140 °C within 60 min, and the dehydrogenation product is completely hydrogenated at 100 °C within 15 min under 100 bar of hydrogen, exhibiting significantly improved desorption/absorption kinetics. No capacity loss is observed for the nano-TiN@N-C-containing sample within 25 de-/hydrogenation cycles because nano-TiN functions as an active catalyst instead of a precursor. A severe structural distortion with extended bond lengths and reduced bond strengths for Al-H bonding when the [AlH₄]^- group adsorbs on the TiN cluster is demonstrated for the first time by density functional theory calculations, which well-explains the reduced de-/hydrogenation temperatures of the nano-TiN@N-C-containing NaAlH₄. These findings provide new insights into designing and synthesizing high-performance catalysts for hydrogen storage in complex hydrides.