Efficient Subnanometric Gold-Catalyzed Hydrogen Generation via Formic Acid Decomposition under Ambient Conditions

Formic acid (FA) has tremendous potential as a safe and convenient source of hydrogen for sustainable chemical synthesis and renewable energy storage, but controlled and efficient dehydrogenation of FA by a robust solid catalyst under ambient conditions constitutes a major challenge. Here, we report that a previously unappreciated combination of subnanometric gold and an acid-tolerant oxide support facilitates the liberation of CO-free H₂ from FA. Applying an ultradispersed gold catalyst comprising TEM-invisible gold subnanoclusters deposited on zirconia to a FA-amine mixture affords turnover frequencies (TOFs) up to 1590 per hour and a turnover number of more than 118 400 at 50 °C. The reaction was accelerated at higher temperatures, but even at room temperature, a significant H₂ evolution (TOFs up to 252 h^–1 after 20 min) can still be obtained. Preliminary mechanistic studies suggest that the reaction is unimolecular in nature and proceeds via a unique amine-assisted formate decomposition mechanism on Au–ZrO₂ interface.