Studies On The Iron-Catalyzed Hydrogenation Of Carbon Dioxide And Formic Ester Derivatives

Carbon dioxide is not only the main greenhouse gas, but also a kind of cheap and available C1 resource. The comprehensive utilization of carbon dioxide and its emission reduction have become great opportunities and challenges that the human society have to face for the sustainable development. But its thermodynamic stability lead to a larger energy input for activation. So how to efficiently implement chemical conversion of carbon dioxide has been a major challenge in the field of catalysis and synthesis.Formic acid is not only an important organic chemical raw material, but is expected to be used as a hydrogen storage material and used in fuel cells. The catalytic hydrogenation of carbon dioxide preparing formic acid has been widely studied, and the catalyst is the key to promote further development in this reaction. At present the research of the catalysts are mainly concentrated in the precious metal catalyst, and the study of the first department of transition metal catalysts are less. We synthesized a series of tricarbonyl(η4-cyclopentadienone) iron complexes, and applied them to the hydrogenation of NaHCO3 successfully. Then, by adjusting the PH value, we successfully achieved the efficient catalytic hydrogenation of carbon dioxide. At last, we have created a new chiral water-soluble iron catalyst Ⅱ-4, and the catalyst can realize the catalytic hydrogenation of NaHCO3 preparing formate with pure water as the solvent. Despite its catalytic activity needs to be improved, the research lays a certain foundation for the further development of other high efficient water-soluble iron catalysts.Methanol is widely used as basic organic chemical raw material and important fuel. In view of the important application prospect and value of methanol, developing a simple and efficient synthetic method has an important theoretical and practical significance. Catalytic hydrogenation of formic esters can provide an important route to prepare methanol. We successfully realized the efficient catalytic hydrogenation of series of formic ester derivatives to produce methanol under mild reaction conditions applying the air-stable dicarbonyl (pyridine) (η4-cyclopentadienone) iron complex Ⅲ-3. The study also lays an important foundation for us to develop other cheap catalyst system in the catalytic hydrogenation of carbon dioxide.