In situ FTIR study of CO2 reduction on inorganic analogues of carbon monoxide dehydrogenase

Abstract

The CO₂-to-CO reduction by carbon monoxide dehydrogenase (CODH) with a [NiFe₄S₄] cluster is considered to be the oldest pathway of biological carbon fixation and therefore may have been involved in the origin of life. Although previous studies have investigated CO₂ reduction by Fe and Ni sulfides to identify the prebiotic origin of the [NiFe₄S₄] cluster, the reaction mechanism remains largely elusive. Herein, we applied in situ electrochemical ATR-FTIR spectroscopy to probe the reaction intermediates of greigite (Fe₃S₄) and violarite (FeNi₂S₄). Intermediate species assignable to surface-bound CO₂ and formyl groups were found to be stabilized in the presence of Ni, lending insight into its role in enhancing the multistep CO₂ reduction process.