Reversible hydrogenation of carbon dioxide to formic acid using a Mn-pincer complex in the presence of lysine

Efficient hydrogen storage and release are essential for effective use of hydrogen as an energy carrier. In principle, formic acid could be used as a convenient hydrogen storage medium via reversible CO₂ hydrogenation. However, noble metal-based catalysts are currently needed to facilitate the (de)hydrogenation, and the CO₂ produced during hydrogen release is generally released, resulting in undesirable emissions. Here we report an α-amino acid-promoted system for reversible CO₂ hydrogenation to formic acid using a Mn-pincer complex as a homogeneous catalyst. We observe good stability and reusability of the catalyst and lysine as the amino acid at high productivities (CO₂ hydrogenation: total turnover number of 2,000,000; formic acid dehydrogenation: total turnover number of 600,000). Employing potassium lysinate, we achieve >80% H₂ evolution efficiency and >99.9% CO₂ retention in ten charge–discharge cycles, avoiding CO₂ re-loading steps between each cycle. This process was scaled up by a factor of 18 without obvious drop of the productivity.