Towards Hydrogen Storage through an Efficient Ruthenium‐Catalyzed Dehydrogenation of Formic Acid

Hydrogen is of fundamental importance for the construction of modern clean‐energy supply systems. In this context, the catalytic dehydrogenation of formic acid (FA) is a convenient method to generate H 2 gas from an easily available liquid. One of the issues associated with current catalytic dehydrogenation systems is insufficient stability. Here, we present a robust and recyclable system for FA dehydrogenation by combining a ruthenium 1,1,1‐tris(diphenylphosphinomethyl)ethane complex and aluminum trifluoromethanesulfonate (Al(OTf) 3 ). This robust system allows steady H 2 production under pressure and recycling for an additional 14 runs without any apparent loss of activity (turnover frequencies up to 1920 h −1 , turnover numbers up to 20 000). Notably, the catalyst can also be used for the dehydrogenation of formates and the reverse hydrogenation of bicarbonates and CO 2 .