Phase controlled synthesis of transition metal carbide nanocrystals by ultrafast flash Joule heating.

Nanoscale carbides enhance ultra-strong ceramics and show activity as high-performance catalysts. Traditional lengthy carburization methods for carbide syntheses usually result in coked surface, large particle size, and uncontrolled phase. Here, a flash Joule heating process is developed for ultrafast synthesis of carbide nanocrystals within 1 s. Various interstitial transition metal carbides (TiC, ZrC, HfC, VC, NbC, TaC, CrC, MoC, and WC) and covalent carbides (BC and SiC) are produced using low-cost precursors. By controlling pulse voltages, phase-pure molybdenum carbides including β-MoC and metastable α-MoC and η-MoC are selectively synthesized, demonstrating the excellent phase engineering ability of the flash Joule heating by broadly tunable energy input that can exceed 3000 K coupled with kinetically controlled ultrafast cooling (>10 K s). Theoretical calculation reveals carbon vacancies as the driving factor for topotactic transition of carbide phases. The phase-dependent hydrogen evolution capability of molybdenum carbides is investigated with β-MoC showing the best performance.