Phenothiazine Derivative-Accelerated Microbial Extracellular Electron Transfer in Bioelectrochemical System

In bioelectrochemical system (BES) the extracellular electron transfer (EET) from bacteria to anode electrode is recognized as a crucial step that governs the anodic reaction efficiency. Here, we report a novel approach to substantially enhance the microbial EET by immobilization of a small active phenothiazine derivative, methylene blue, on electrode surface. A comparison of the currents generated by Shewanella oneidensis MR-1 and its mutants as well as the electrochemical analytical results reveal that the accelerated EET was attributed to enhanced interactions between the bacterial outer-membrane cytochromes and the immobilized methylene blue. A further investigation into the process using in situ Raman spectro-electrochemical method coupled with density functional theory calculations demonstrates that the electron shuttling was achieved through the change of the molecule conformation of phenothiazine in the redox process. These results offer useful information for engineering BES.