Bio-inspired CO₂conversion by iron sulfide catalysts under sustainable conditions

Abstract

The mineral greigite presents similar surface structures to the active sites found in many modern-day enzymes. We show that particles of greigite can reduce CO2 under ambient conditions into chemicals such as methanol, formic, acetic and pyruvic acid. Our results also lend support to the Origin of Life theory on alkaline hydrothermal vents.

Early Microbial Evolution: The Age of Anaerobes

“…Furthermore, the latest laboratory simulations are also of interest in this respect. Roldan et al (2015) reported the laboratory synthesis of formate, acetate, methanol, and pyruvate from CO 2 using gregite (Fe 3 S 4 ) as a catalyst under simulated alkaline hydrothermal vent conditions; that is exciting because the carbon species obtained very closely resemble the first steps of CO 2 fixation in the acetyl-CoA pathway (Fuchs 2011). Yamaguchi et al (2014) reported the FeNiS-catalyzed synthesis of CO and methane under simulated alkaline vent conditions, while Herschy et al (2014) obtained CO and formaldehyde.…”

Hydrogen Generation from Additive-Free Formic Acid Decomposition Under Mild Conditions by Pd/C: Experimental and DFT Studies

“…More importantly, if the production of formic acid can be carried out under mild conditions via biomass conversion, a carbon neutral hydrogen storage cycle can be completed [20]. The proposed cycle can be closed when CO 2 evolved during dehydrogenation of formic acid is reduced with an external supply of low purity H 2 [21]. Formic acid decomposition occurs by two different pathways: dehydrogenation (1) and dehydration (2).…”

Activation and dissociation of CO2 on the (001), (011), and (111) surfaces of mackinawite (FeS): A dispersion-corrected DFT study

“…26 Ironnickel sulfide membranes formed in hydrothermal systems in the deep ocean floor are increasingly considered to be the early catalysts for a series of biochemical reactions leading to the emergence of life. [27][28][29][30] The anaerobic production of acetate, formaldehyde, and amino acids, and the nucleic acid bases (the organic precursors for larger biomolecules) are thought to have been catalyzed by small cubane (Fe, Ni)S clusters (for example, Fe 5 NiS 8 ), which are structurally similar to the surfaces of present day sulfide minerals such as greigite (Fe 3 S 4 ), 31 violarite (FeNi 2 S 4 ), 32 and mackinawite (FeS). 33,34 In nature, the enzyme, carbon monoxide dehydrogenase (CODH), which has its primary active site as (Fe, Ni)S clusters, has been shown to efficiently and reversibly catalyze the reduction of CO 2 to CO. 35,36 Huber and Wächtershäuser demonstrated that it is possible to synthesize acetic acid on sulfide surfaces in conditions simulating Earth before life, 37 whereas a recent study has shown that Fe 3 S 4 acts like a catalyst in the electro-reduction of CO 2 to methanol, and formic, acetic, and pyruvic acids under moderate conditions of pressure and temperature.…”

“…33,34 In nature, the enzyme, carbon monoxide dehydrogenase (CODH), which has its primary active site as (Fe, Ni)S clusters, has been shown to efficiently and reversibly catalyze the reduction of CO 2 to CO. 35,36 Huber and Wächtershäuser demonstrated that it is possible to synthesize acetic acid on sulfide surfaces in conditions simulating Earth before life, 37 whereas a recent study has shown that Fe 3 S 4 acts like a catalyst in the electro-reduction of CO 2 to methanol, and formic, acetic, and pyruvic acids under moderate conditions of pressure and temperature. 31 In this study, we report the reactivity of the iron sulfide FeS towards the adsorption, activation, and reduction of CO 2 using first-principles density functional theory (DFT) calculations. FeS is a layered iron sulfide mineral that crystallises in the tetragonal structure, and it is considered to be the first iron sulfide phase formed from the reaction of Fe and S in low temperature aqueous environments.…”