RESUMEN

The Fischer-Tropsch (FT) process converts a mixture of CO and H2 into liquid hydrocarbons as a major component of the gas-to-liquid technology for the production of synthetic fuels. Contrary to the energy-demanding chemical FT process, the enzymatic FT-type reactions catalyzed by nitrogenase enzymes, their metalloclusters, and synthetic mimics utilize H+ and e- as the reducing equivalents to reduce CO, CO2, and CN- into hydrocarbons under ambient conditions. The C1 chemistry exemplified by these FT-type reactions is underscored by the structural and electronic properties of the nitrogenase-associated metallocenters, and recent studies have pointed to the potential relevance of this reactivity to nitrogenase mechanism, prebiotic chemistry, and biotechnological applications. This review will provide an overview of the features of nitrogenase enzymes and associated metalloclusters, followed by a detailed discussion of the activities of various nitrogenase-derived FT systems and plausible mechanisms of the enzymatic FT reactions, highlighting the versatility of this unique reactivity while providing perspectives onto its mechanistic, evolutionary, and biotechnological implications.

Asunto(s)

Hidrocarburos , Nitrogenasa , Nitrogenasa/química , Hidrocarburos/química , Biotecnología

RESUMEN

The Fe protein of nitrogenase plays multiple roles in substrate reduction and metallocluster assembly. Best known for its function to transfer electrons to its catalytic partner during nitrogenase catalysis, the Fe protein is also a key player in the biosynthesis of the complex metalloclusters of nitrogenase. In addition, it can function as a reductase on its own and affect the ambient reduction of CO2 or CO to hydrocarbons. This review will provide an overview of the properties and functions of the Fe protein, highlighting the relevance of this unique FeS enzyme to areas related to the catalysis, biosynthesis, and applications of the fascinating nitrogenase system.

Asunto(s)

Dióxido de Carbono , Nitrogenasa , Dióxido de Carbono/química , Hidrocarburos , Nitrogenasa/metabolismo , Oxidación-Reducción , Oxidorreductasas/metabolismo

RESUMEN

Sulfur-assisted corrosion is a process known to material scientists for many decades now. Though the corrosion of iron in the presence of sulfur has been studied extensively, it has never been used to intentionally synthesize mackinawite. In contrast to the conventional preparation of mackinawite by precipitation, the synthesis from the elements can be carried out without additional ions. This makes it possible to investigate the influence of any dissolved salts on the mackinawite formation and its properties. We found that the addition of NaCl significantly accelerates the reaction and furthermore influences the Fe2+ ion content of the formed mackinawite itself. This finding leads us to propose a novel model of charged layers which can be used to explain some of the inconsistencies found in the literature regarding the structure and particle characteristics of nano-mackinawite.