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Immobilization of O2-tolerant [NiFe] hydrogenase from Cupriavidus necator on Tin-rich Indium Oxide Alters the Catalytic Bias from H2 Oxidation to Proton Reduction

Davis, Victoria ; Heidary, Nina ; Guiet, Amandine ; Ly, Khoa Hoang ; Zerball, Maximilian ; Schulz, Claudia ; Michael, Norbert ; Klitzing, Regine von ; Hildebrandt, Peter ; Frielingsdorf, Stefan ; Lenz, Oliver ; Zebger, Ingo ; Fischer, Anna (2023)
Immobilization of O2-tolerant [NiFe] hydrogenase from Cupriavidus necator on Tin-rich Indium Oxide Alters the Catalytic Bias from H2 Oxidation to Proton Reduction.
In: ACS Catalysis, 13
doi: 10.1021/acscatal.2c06334
Article, Bibliographie

Abstract

The ability of hydrogenases to reversibly catalyze the production and oxidation of hydrogen with minimal overpotential makes them attractive electrocatalysts for hydrogen energy conversion devices. The oxygen tolerance demonstrated by the membrane-bound [NiFe] hydrogenase (MBH) from Cupriavidus necator (previously known as Ralstonia eutropha) provides a further advantage; however, this enzyme is well-known as being strongly biased toward hydrogen oxidation and shows little promise toward hydrogen production. Here, we have immobilized the MBH after genetically attaching two different affinity tags to the C terminus of the enzyme─a His-tag (MBHHis) and a Strep-tag (MBHStrep). The differences in adsorption and electrocatalytic behavior were investigated when wired to an amorphous, transparent, and planar tin-rich indium tin oxide (ITOTR) thin-film electrode with a Sn/In ratio of 1:1. As demonstrated by ATR–IR spectroelectrochemical studies, the affinity of the His-tag for the tin-rich ITO surface allows for quantitative immobilization of MBHHis in a direct electron transfer configuration. Remarkably, once immobilized on tin-rich ITO, hydrogen oxidation as well as an unusually high proton reduction current is observed especially under hydrogen. While this behavior is only observed for tin-rich ITO (as compared to classical crystalline ITO, with a lower tin content) and not fully understood so far, the conditions demonstrated herein promote catalytic bidirectionality in essentially unidirectional [NiFe] hydrogenases, and that is at least partially related to favorable, direct enzyme–semiconductor interactions.

Item Type: Article
Erschienen: 2023
Creators: Davis, Victoria ; Heidary, Nina ; Guiet, Amandine ; Ly, Khoa Hoang ; Zerball, Maximilian ; Schulz, Claudia ; Michael, Norbert ; Klitzing, Regine von ; Hildebrandt, Peter ; Frielingsdorf, Stefan ; Lenz, Oliver ; Zebger, Ingo ; Fischer, Anna
Type of entry: Bibliographie
Title: Immobilization of O2-tolerant [NiFe] hydrogenase from Cupriavidus necator on Tin-rich Indium Oxide Alters the Catalytic Bias from H2 Oxidation to Proton Reduction
Language: English
Date: 24 April 2023
Publisher: ACS Publications
Journal or Publication Title: ACS Catalysis
Volume of the journal: 13
DOI: 10.1021/acscatal.2c06334
Abstract:

The ability of hydrogenases to reversibly catalyze the production and oxidation of hydrogen with minimal overpotential makes them attractive electrocatalysts for hydrogen energy conversion devices. The oxygen tolerance demonstrated by the membrane-bound [NiFe] hydrogenase (MBH) from Cupriavidus necator (previously known as Ralstonia eutropha) provides a further advantage; however, this enzyme is well-known as being strongly biased toward hydrogen oxidation and shows little promise toward hydrogen production. Here, we have immobilized the MBH after genetically attaching two different affinity tags to the C terminus of the enzyme─a His-tag (MBHHis) and a Strep-tag (MBHStrep). The differences in adsorption and electrocatalytic behavior were investigated when wired to an amorphous, transparent, and planar tin-rich indium tin oxide (ITOTR) thin-film electrode with a Sn/In ratio of 1:1. As demonstrated by ATR–IR spectroelectrochemical studies, the affinity of the His-tag for the tin-rich ITO surface allows for quantitative immobilization of MBHHis in a direct electron transfer configuration. Remarkably, once immobilized on tin-rich ITO, hydrogen oxidation as well as an unusually high proton reduction current is observed especially under hydrogen. While this behavior is only observed for tin-rich ITO (as compared to classical crystalline ITO, with a lower tin content) and not fully understood so far, the conditions demonstrated herein promote catalytic bidirectionality in essentially unidirectional [NiFe] hydrogenases, and that is at least partially related to favorable, direct enzyme–semiconductor interactions.

Divisions: 05 Department of Physics
05 Department of Physics > Institute for condensed matter physics (2021 merged in Institute for Condensed Matter Physics)
Date Deposited: 04 May 2023 08:18
Last Modified: 31 Jul 2023 08:35
PPN: 510031773
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