Enzymatic Hydrogen Electrosynthesis at Enhanced Current Density Using a Redox Polymer

Abstract

High-temperature tolerant enzymes offer multiple advantages over enzymes from mesophilic organisms for the industrial production of sustainable chemicals due to high specific activities and stabilities towards fluctuations in pH, heat, and organic solvents. The production of molecular hydrogen (H2) is of particular interest because of the multiple uses of hydrogen in energy and chemicals applications, and the ability of hydrogenase enzymes to reduce protons to H2 at a cathode. We examined the activity of Hydrogen-Dependent CO2 Reductase (HDCR) from the thermophilic bacterium Thermoanaerobacter kivui when immobilized in a redox polymer, cobaltocene-functionalized polyallylamine (Cc-PAA), on a cathode for enzyme-mediated H2 formation from electricity. The presence of Cc-PAA increased reductive current density 340-fold when used on an electrode with HDCR at 40 °C, reaching unprecedented current densities of up to 3 mA·cm−2 with minimal overpotential and high faradaic efficiency. In contrast to other hydrogenases, T. kivui HDCR showed substantial reversibility of CO-dependent inactivation, revealing an opportunity for usage in gas mixtures containing CO, such as syngas. This study highlights the important potential of combining redox polymers with novel enzymes from thermophiles for enhanced electrosynthesis.

The hydrogen-dependent CO2 reductase from Acetobacterium woodii and Thermoanaerobacter kivui : Capture and storage of hydrogen and carbon dioxide in formic acid by acetogenic bacteria

“…Apparently, CO-binding to the H-cluster did not result in an irreversible damage of the oxidation state (Hred) of the H-cluster, which was shown in other CO inhibition studies for [FeFe]-hydrogenases before (Goldet et al, 2009;Baffert et al, 2011;Foster et al, 2012). Noteworthy, the HDCR from T. kivui also showed a substantial reversibility of CO-dependent inactivation in enzymatic electrosynthesis experiments (Ruth et al, 2021).…”

A purified energy-converting hydrogenase from Thermoanaerobacter kivui demonstrates coupled H+-translocation and reduction in vitro

“…S4). Indeed, the enzyme was inhibited by CO and 50% inhibition was observed with 204.7 ± 5.3 μM CO, indicating a high tolerance for CO in vitro, compared with other hydrogenases (13,16,42). Last, we assessed the impact of ions on the Fd 2-:H + oxidoreductase activity.…”

Towards an accelerated decarbonization of the chemical industry by electrolysis

“…59 In the field of hydrogen production, numerous enzyme-electroreduction systems were investigated for their potential to deliver improvement in energy efficiency. [60][61][62] Hardt et al 63 reported an example of such enzymatic systems (hydrogenase embedded in a hydrogel), allowing production of hydrogen with only 12 mV overpotential.…”