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Bioelectrocatalytic synthesis is the conversion of electrical energy into value‐added products using biocatalysts. These methods merge the specificity and selectivity of biocatalysis and energy‐related electrocatalysis to address challenges in the sustainable synthesis of pharmaceuticals, commodity chemicals, fuels, feedstocks and fertilizers. However, the specialized experimental setups and domain knowledge for bioelectrocatalysis pose a significant barrier to adoption. This review introduces key concepts of bioelectrosynthetic systems. We provide a tutorial on the methods of biocatalyst utilization, the setup of bioelectrosynthetic cells, and the analytical methods for assessing bioelectrocatalysts. Key applications of bioelectrosynthesis in ammonia production and small‐molecule synthesis are outlined for both enzymatic and microbial systems. This review serves as a necessary introduction and resource for the non‐specialist interested in bioelectrosynthetic research. [ABSTRACT FROM AUTHOR]

Although the past 20 years have seen significant advances in tailoring materials for improving the performance of bioelectrochemical systems, recently, there have been efforts in utilizing the synthetic biology toolkit for engineering organisms for bioelectrochemical systems. This review discusses the use of synthetic biology to engineer non‐native properties into bioelectrochemical systems for increasing the diversity of fuel utilization in energy applications, allowing for novel electrosynthetic strategies, and improving the selectivity of biosensors. The review also discusses synthetic biology strategies for improving the abiotic/biotic interface, which improves the performance of bioelectrochemical systems. Both strategies are required and need to be combined with materials innovation to produce commercially viable bioelectrochemical systems in the future. [ABSTRACT FROM AUTHOR]

The ability to establish successful and efficient extracellular electron transfer (EET) between bacteria and electrode surfaces is critical for the development of mediated microbial electrochemical technologies. Here, we describe a phenazine-based mediator system to facilitate electron transfer from the model bacterium Escherichia coli during glucose metabolism. Phenazine redox mediators were experimentally evaluated, demonstrating distinct mediated currents, dependent on mediator structure. Our results show that the choice of a mediator with the appropriate redox potential is not the single aspect to consider when rationally designing future mediator-based EET systems. [ABSTRACT FROM AUTHOR]

Over the past two decades, the designs of redox polymers have become critical to the field of mediated bioelectrocatalysis and are used in commercial glucose biosensors, as well as other bioelectrochemical applications (e.g., energy harvesting). These polymers are specifically used to immobilize redox mediators on electrode surfaces, allowing for self-exchange-based conduction of electrons from enzymes far from the electrode to the electrode surface. However, the synthesis of redox polymers is challenging and results in large batch-to-batch variability. Herein, we report a rapid entrapment of mediators for NAD + -dependent bioelectrocatalysis within reverse ionically condensed polyelectrolytes. A high ionic strength aqueous solution of oppositely charged polyelectrolytes, composed of cationic polyguanidinium (PG) chloride and anionic sodium hexametaphosphate (P6), undergoes phase inversion into a solid microporous polyelectrolyte complex (PEC) when introduced into a low ionic strength aqueous solution. The ionic strength-triggered phase inversion of PGP6 solutions was investigated as a means to entrap mediators on the surface of electrodes for mediated bioelectrocatalysis. Compared to the traditional cross-linked immobilizations using redox polymers, this phase inversion takes place within seconds and requires up to 60 min for complete stabilization. In this work, redox mediator phenazine ethosulfate (PES) was entrapped within PGP6 on electrode surfaces for nicotinamide adenine dinucleotide (NAD + )-dependent bioelectrocatalysis. In the bulk solution, NAD + -dependent dehydrogenase enzymes catalyze the oxidation of the substrate while reducing NAD to reduced nicotinamide adenine dinucleotide (NADH). The resulting NADH is reoxidized to NAD + by the entrapped PES that gets reduced on the electrode, completing the NAD + -regeneration-based bioelectrocatalysis. To show the use of these new materials in an application, biofuel cells were evaluated using four different anodic enzyme systems (alcohol dehydrogenase, lactate hydrogenase, glycerol dehydrogenase, and glucose dehydrogenase).