Low-temperature aqueous-phase dehydrogenation of methanol catalyzed by synergistic Ir single-atom and cluster dual sites.

Aqueous-phase reforming of methanol (APRM) offers a promising route for efficient hydrogen generation and safe transportation, yet it typically requires harsh conditions (above 200°C, 25-50 bar) and energy-intensive purification. Here, we report a heterogeneous catalyst featuring synergistic Ir single-atom and cluster dual sites that enables efficient hydrogen production from methanol and water at record-low temperatures (75°C-95°C) and ambient pressure. This unique ensemble effect drives a tandem reaction pathway, with Ir clusters promoting methanol dehydrogenation to formic acid, while adjacent Ir single atoms facilitate rapid formic acid decomposition into H2 and CO2 to suppress CO intermediates. As a result, the developed catalyst achieves a remarkable hydrogen production rate of 346.9 molH2 molIr -1 h-1 and 100% H2 selectivity with no detectable CO formation. To the best of our knowledge, this represents one of the lowest temperature ranges demonstrated for efficient methanol-to-hydrogen conversion via heterogeneous catalysis, advancing methanol as a practical liquid H2 carrier for on-demand high-purity hydrogen production.