Electrochemical Additive Manufacturing of Living Bioelectrodes Having Intimate Electronic Couplings between Exoelectrogens and Electrodes

Engineered Living Materials (ELMs) represent a pioneering approach that blends living organisms with inanimate components to deliver specific responsive functionalities, addressing pressing challenges in conventional materials and devices. Through the innovative integration of living exoelectrogens, electrochemically active microorganisms, into a redox‐active matrix, ELMs harmonize microbial electrochemical processes with the imperatives of environmental remediation and sustainable energy recovery on a scalable platform. However, this technology grapples with an intrinsic challenge at the intersection of the biological and abiotic realms, coupled with constraints in achieving reliable, reproducible, and programmable manufacturing processes. In this study, we present a breakthrough in the form of highly efficient, remarkably electrocatalytic, and substantial bioelectrodes. These bioelectrodes can be mass‐produced using cutting‐edge biomanufacturing techniques. Their significant thickness and diverse shapes are achieved through an electrochemically driven 3‐D printing process employing a living microbe‐infused polymer ink. Powered by a custom‐made 3‐D printer equipped with electropolymerization controls, this automated, batch‐fabricable, scalable, and template‐free construction method opens new horizons for creating electrochemically active organic bioelectrodes, ushering in a novel era for ELM technology. The electropolymerized poly(3,4‐ethylenedioxythiophene) (PEDOT) serves as a pivotal conductor, facilitating the extracellular transfer of electrons between metabolically active exoelectrogens and the external abiotic systems. Importantly, this process is executed without compromising bacterial viability and function over an extended duration. Moreover, the resultant ELM network exhibits exceptional permeability to light and gases, along with the capacity to maintain a thermal gradient. These attributes collectively pave the way for transformative breakthroughs in the realms of bioelectronics, bioenergy, and biosensors. This article is protected by copyright. All rights reserved.