Electrochemical CO2 Reduction by Ni-containing Iron Sulfides: How Is CO2 Electrochemically Reduced at Bisulfide-Bearing Deep-sea Hydrothermal Precipitates?

Abstract

The discovery of deep-sea hydrothermal vents on the late 1970's has led to many hypotheses concerning chemical evolution in the prebiotic ocean and the early evolution of energy metabolism in ancient Earth. Such studies stand on the quest for the bioenergetic evolution to utilize reducing chemicals such as H2 for CO2 reduction and carbon assimilation. In addition to the direct reaction of H2 and CO2, the electrical current passing across a bisulfide-bearing chimney structure has pointed to the possible electrocatalytic CO2 reduction at the cold ocean-vent interface (R. Nakamura, et al. Angew. Chem. Int. Ed. 2010, 49, 7692−7694). To confirm the validity of this hypothesis, here, we examined the energetics of electrocatalytic CO2 reduction by iron sulfide (FeS) deposits at slightly acidic pH. Although FeS deposits inefficiently reduced CO2, the efficiency of the reaction was substantially improved by the substitution of Fe with Ni to form FeNi2S4 (violarite), of which surface was further modified with amine compounds. The potential-dependent activity of CO2 reduction demonstrated that CO2 reduction by H2 in hydrothermal fluids was involved in a strong endergonic electron transfer reaction, suggesting that a naturally occurring proton-motive force (PMF) as high as 200mV would be established across the hydrothermal vent chimney wall. However, in the chimney structures, H2 generation competes with CO2 reduction for electrical current, resulting in rapid consumption of the PMF. Therefore, to maintain the PMF and the electrosynthesis of organic compounds in hydrothermal vent mineral deposits, we propose a homeostatic pH regulation mechanism of FeS deposits, in which elemental hydrogen stored in the hydrothermal mineral deposits is used to balance the consumption of the electrochemical gradient by H2 generation.