Active N dopant states of electrodes regulate extracellular electron transfer of Shewanella oneidensis MR-1 for bioelectricity generation: Experimental and theoretical investigations

Anodic N doping is an effective way to improve power generation of bioelectrochemical systems (BESs), but the role of various active N dopant states of the anode on BES performance is still unclear. Herein, the effect of anodic active N dopant states on bioelectricity generation of Shewanella oneidensis MR-1 inoculated BESs particularly including microbial extracellular electron transfer (EET) was explored using experiments and theoretical simulations. It was found a positive linear correlation between the peak current density of BESs and pyrrolic N content of the anode, which would mainly ascribe to the enhancement of both direct electron transfer (DET) and mediated electron transfer (MET) of S. oneidensis MR-1. Morever, the molecule dynamic simulation revealed that such EET improvements of S. oneidensis MR-1 could be due to more remarkable reduction in the thermodynamic and kinetic resistances of the DET and MET processes with anodic doping of pyrrolic N compared to pyridinic N and graphitic N. This work provides a valuable guideline to design of high-performance anodes for potential BES applications.