Continuous Hydrogen Generation from Formic Acid: Highly Active and Stable Ruthenium Catalysts

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Abstract
The ruthenium‐catalyzed decomposition of formic acid was investigated with respect to continuous hydrogen generation and long‐term stability of the catalytic systems. A highly active and stable system is presented, which was studied in batch and continuous modes for up to two months. The optimized catalyst system containing N,N‐dimethyl‐n‐hexylamine with an in situ generated catalyst from (benzene)ruthenium dichloride dimer [RuCl2(benzene)]2 and 6 equivalents of 1,2‐bis(diphenylphosphino)ethane (dppe) reached at room temperature a total turnover number (TON) of approximatly 260,000 with average turnover frequency (TOF) of about 900 h−1. Only hydrogen and carbon dioxide were detected in the produced gas mixture which makes this system applicable for direct use in fuel cells.

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