Recent Developments in Reversible CO2 Hydrogenation and Formic Acid Dehydrogenation over Molecular Catalysts.

Carbon dioxide (CO2), a valuable feedstock, can be reutilized as a hydrogen carrier by hydrogenating CO2 to formic acid (FA) and releasing hydrogen by FA dehydrogenation in a reversible manner. Notably, FA is liquid at room temperature and can be stored and transported considerably more safely than hydrogen gas. Herein, we extensively reviewed transition-metal-based molecular catalysts explored for reversible CO2 hydrogenation and FA dehydrogenation. This Review describes different approaches explored for carbon-neutral hydrogen storage and release by applying CO2 hydrogenation to FA/formate and the subsequent release of H2 by the dehydrogenation of FA over a wide range of molecular catalysts based on noble and non-noble metals. Emphasis is also placed on the specific catalyst-to-substrate interaction by highlighting the specific role of the catalyst in the CO2 hydrogenation-FA dehydrogenation pathway.

Diruthenium Catalyst for Hydrogen Production from Aqueous Formic Acid.

Diruthenium complexes [{(η6-arene)RuCl}2(µ-κ2:κ2-benztetraimd)]2+ containing the bridging bis-imidazole methane-based ligand {1,4-bis(bis(2-ethyl-5-methyl-1H-imidazol-4-yl)methyl)benzene} (benztetraimd) are synthesized for catalytic formic acid dehydrogenation in water at 90 °C. Catalyst [{(η6-p-cymene)RuCl}2(µ-κ2:κ2-benztetraimd)]2+ [1-Cl2] exhibited a remarkably high turnover frequency (1993 h-1 per Ru atom) and long-term stability over 60 days for formic acid dehydrogenation, while the analogous (η6-benzene)diruthenium and mononuclear catalysts displayed low activity with poor long-term stability. Notably, catalyst [1-Cl2] also displayed an appreciably high turnover number of 93 200 for the bulk-scale reaction. In addition, the in-depth mass and nuclear magnetic resonance investigations under the catalytic and control experimental conditions revealed the active involvement of several crucial catalytic intermediate species, such as Ru-aqua species [{(η6-p-cymene)Ru(H2O)}2(µ-L)]2+ [1-(OH2)2], Ru-formato species [{(η6-p-cymene)Ru(HCOO)}2(µ-L)] [1-(HCOO)2], and Ru-hydrido species [{(η6-p-cymene)Ru(H)}2(µ-L)] [1-(H)2], in the catalytic formic acid dehydrogenation reaction.