Highly efficient heterogeneous thermal catalysis for noble-metal-free hydrogen production from formic acid

Hydrogen extraction from liquid hydrogen carriers is a promising strategy to address hydrogen storage and transportation challenges for a hydrogen economy. We report a novel heterogeneous catalytic architecture, Ni(Mn)-O-P/GaN nanowires, for efficient, selective, and ultra-stable hydrogen evolution from formic acid (FA). The catalyst achieves a high activity of 29.92 mol H₂·g_cat^-1·h^-1 with nearly 100% selectivity and a high turnover frequency (TOF) of 31,019.2 h^-1 at 150 °C. It exhibits exceptional stability over 4000 hours under fluctuated temperatures (55-75 °C) with a turnover numbers (TONs) of 5,023,060, integrable with low-grade industrial waste heat. In-situ characterizations, isotope experiments, and density functional theory calculations collectively reveal that the synergy between Ni(Mn)-O-P and GaN are favorable for the O-H dissociation of FA with an interesting H-exchange mechanism with H₂O while inhibiting the undesired FA dehydration and coking formation. An industrial prototype test validates practical on-demand hydrogen production using waste heat.