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The development of bioelectrochemical systems requires careful selection of both their biotic and abiotic components to obtain sustainable devices. Herein, we report a biophotoelectrode obtained with polyhydroxybutyrate (PHB), a biopolymer, which purple non-sulphur bacteria produce as an energy stock under specific environmental conditions. The electrode was obtained by casting a mixture composed of PHB and carbon fibers in a 3:2 mass ratio. Following, the composite material was modified with polydopamine and thermally treated to obtain a hydrophilic electrode with improved electrochemical behavior. The bio-based electrode was tested with metabolically active cells of Rhodobacter capsulatus embedded in a biohybrid matrix of polydopamine. The system achieved enhanced catalytic activity under illumination, with an 18-fold increase in photocurrent production compared to biophotoelectrodes based on glassy carbon, reaching a current density of 12 ± 3 μ A cm−2, after 30 min of light exposure at +0.32 V. The presented biocompatible electrode provides a sustainable alternative to metal-based and critical raw material-based electrodes for bioelectrochemical systems. [ABSTRACT FROM AUTHOR]

We report the preparation of mono and bi-enzymatic bioanodes immobilizing dehydrogenase enzymes at the surface of a carbon support aiming to follow the 2 and 4 electron transfer of ethanol oxidation by HPLC. Enzymatic immobilization of ADH and AlDH enzymes at the bioanodes was performed using Nafion membranes modified with tetrabutylammonium salt. Themonoenzymatic film with immobilized alcohol dehydrogenase (ADH) provided, at pH 8.50, power densities of 29.5 ± 3.4 μW cm-2; however, addition of the second enzyme (AlDH) aiming to transfer 4 electrons furnished values as high as 186.0 ± 19.4 μW cm-2. These results indicate that as the product of the first oxidation is consumed by the second enzyme it inhibits the first enzyme less thus, furnishing better performance for the bienzymatic electrodes. Long-term electrolysis (12 hours) of ethanol followed by HPLC-UV/RID system confirms our electrochemical finding demonstrating formation of 2 and 4 electrons products, e.g., acetaldehyde (6.6 mmol L-1) and acetate (0.72 mmol L-1) when a two dehydrogenase enzyme system was employed. The faradaic efficiency was above 60% for the bi-enzymatic system. We demonstrate that simultaneous product identification and mass balance analysis is an important tool to follow the synergy between the enzymes within the enzymatic cascade. [ABSTRACT FROM AUTHOR]