title: Efficient subnanometric gold-catalyzed hydrogen generation via formic acid decomposition under ambient conditions.
abstract: 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 H(2) 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 H(2) 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-ZrO(2) interface.
authors.affiliation: Department of Chemistry, Shanghai Key Laboratory of Molecular Catalysis and Innovative Materials, Fudan University, Shanghai 200433, P. R. China.
authors.forename: Qing-Yuan
authors.initials: QY
authors.lastname: Bi
authors.forename: Xian-Long
authors.initials: XL
authors.lastname: Du
authors.forename: Yong-Mei
authors.initials: YM
authors.lastname: Liu
authors.forename: Yong
authors.initials: Y
authors.lastname: Cao
authors.forename: He-Yong
authors.initials: HY
authors.lastname: He
authors.forename: Kang-Nian
authors.initials: KN
authors.lastname: Fan