On the Mediated Electron Transfer of Immobilized Galactose Oxidase for Biotechnological Applications.

Invited for the cover of this issue are Felipe Conzuelo, Wolfgang Schuhmann, and co-workers at the Ruhr University Bochum. The image depicts the electrochemical conversion of glycerol and 5-(hydroxymethyl)furfural with an electrode made up of galactose oxidase electrically wired with a redox polymer. Read the full text of the article at 10.1002/chem.202200868.

On the Mediated Electron Transfer of Immobilized Galactose Oxidase for Biotechnological Applications.

The use of enzymes as catalysts in chemical synthesis offers advantages in terms of clean and highly selective transformations. Galactose oxidase (GalOx) is a remarkable enzyme with several applications in industrial conversions as it catalyzes the oxidation of primary alcohols. We have investigated the wiring of GalOx with a redox polymer; this enables mediated electron transfer with the electrode surface for its potential application in biotechnological conversions. As a result of electrochemical regeneration of the catalytic center, the formation of harmful H2 O2 is minimized during enzymatic catalysis. The introduced bioelectrode was applied to the conversion of bio-renewable platform materials, with glycerol as model substrate. The biocatalytic transformations of glycerol and 5-hydroxymethylfurfural (HMF) were investigated in a circular flow-through setup to assess the possibility of substrate over-oxidation, which is observed for glycerol oxidation but not during HMF conversion.

Splicing the active phases of copper/cobalt-based catalysts achieves high-rate tandem electroreduction of nitrate to ammonia.

Electrocatalytic recycling of waste nitrate (NO3-) to valuable ammonia (NH3) at ambient conditions is a green and appealing alternative to the Haber-Bosch process. However, the reaction requires multi-step electron and proton transfer, making it a grand challenge to drive high-rate NH3 synthesis in an energy-efficient way. Herein, we present a design concept of tandem catalysts, which involves coupling intermediate phases of different transition metals, existing at low applied overpotentials, as cooperative active sites that enable cascade NO3--to-NH3 conversion, in turn avoiding the generally encountered scaling relations. We implement the concept by electrochemical transformation of Cu-Co binary sulfides into potential-dependent core-shell Cu/CuOx and Co/CoO phases. Electrochemical evaluation, kinetic studies, and in-situ Raman spectra reveal that the inner Cu/CuOx phases preferentially catalyze NO3- reduction to NO2-, which is rapidly reduced to NH3 at the nearby Co/CoO shell. This unique tandem catalyst system leads to a NO3--to-NH3 Faradaic efficiency of 93.3 ± 2.1% in a wide range of NO3- concentrations at pH 13, a high NH3 yield rate of 1.17 mmol cm-2 h-1 in 0.1 M NO3- at -0.175 V vs. RHE, and a half-cell energy efficiency of ~36%, surpassing most previous reports.