In this account the concept of using formic acid as a hydrogen storage material is presented. Catalytic reduction of carbon dioxide and heterogeneously catalyzed decomposition of formic acid to hydrogen and carbon dioxide are briefly discussed. In the main part the historic development and recent examples of homogeneously catalyzed hydrogen generation from formic acid are covered in detail.

Hydrogen represents a clean energy source, which can be efficiently used in fuel cells generating electricity with water as the only byproduct. However, hydrogen generation from renewables under mild conditions and efficient hydrogen storage in a safe and reversible manner constitute important challenges. In this respect formic acid (HCO(2)H) represents a convenient hydrogen storage material, because it is one of the major products from biomass and can undergo selective decomposition to hydrogen and carbon dioxide in the presence of suitable catalysts. Here, the first light-driven iron-based catalytic system for hydrogen generation from formic acid is reported. By application of a catalyst formed in situ from inexpensive Fe(3)(CO)(12), 2,2':6'2''-terpyridine or 1,10-phenanthroline, and triphenylphosphine, hydrogen generation is possible under visible light irradiation and ambient temperature. Depending on the kind of N-ligands significant catalyst turnover numbers (>100) and turnover frequencies (up to 200 h(-1)) are observed, which are the highest known to date for nonprecious metal catalyzed hydrogen generation from formic acid. NMR, IR studies, and DFT calculations of iron complexes, which are formed under reaction conditions, confirm that PPh(3) plays an active role in the catalytic cycle and that N-ligands enhance the stability of the system. It is shown that the reaction mechanism includes iron hydride species which are generated exclusively under irradiation with visible light.

The efficient generation of hydrogen from formic acid/amine adducts at ambient temperature is demonstrated. The highest catalytic activity (TOF up to 3630 h(-1) after 20 min) was observed in the presence of in situ generated ruthenium phosphine catalysts. Compared to the previously known methods to generate hydrogen from liquid feedstocks, the systems presented here can be operated at room temperature without the need for any high-temperature reforming processes, and the hydrogen produced can then be directly used in fuel cells. A variety of Ru precursors and phosphine ligands were investigated for the decomposition of formic acid/amine adducts. These catalytic systems are particularly interesting for the generation of H2 for new applications in portable electric devices.

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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-nhexylamine with an in situ generated catalyst from (benzene)ruthenium dichloride dimer [RuCl 2 A C H T U N G T R E N N U N G (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 À1. Only hydrogen and carbon dioxide were detected in the produced gas mixture which makes this system applicable for direct use in fuel cells.