In Situ Probing the Mass Transport Property Inside an Imitated Three-Dimensional Porous Bioelectrode.

Three-dimensional porous materials have been demonstrated as the most successful bioelectrodes in bioelectrochemical systems due to their high specific surface area and abundant adhesion regions for electroactive bacteria. However, the pore clogging potentially limits the mass transfer process inside the electrode due to the unreasonable structure design and long-term operation. The investigation of mass transport behavior in the porous scaffolds is of great significance for designing the electrode structure and optimizing bioelectrochemical system performance. To in situ characterize the mass transport behavior in the orderly pore structure, model electrodes with 100 copper wires (10 × 10) are constructed to imitate a three-dimensional porous structure (pore size: ∼150 μm) commonly employed in bioelectrodes. The poor proton effective diffusion coefficient solidly demonstrates that the mass transport inside the three-dimensional porous electrode is critically inhibited, leading not only to a progressive change and sparse biomass in the biofilm development process but also to biofilm acidification due to serious proton accumulation. It finally results in sluggish bacterial metabolic activity and a decreased electrocatalytic capacity. The interior space of porous electrodes cannot be adequately utilized, resulting in the inability to fully exploit the advantages of their abundant surface area. Consequently, the construction of gradient porous electrodes with small inner and large outer pores to enhance mass transport is a feasible proposal for enhancing performance. The proposed methodology of establishing model electrodes combined with the in situ detection technique within porous electrodes is crucial for acquiring various types of physicochemical information inside the bioelectrode, such as biofilm growth situation, biochemical reaction conditions, as well as mass transfer characteristics. More importantly, the work provides a fundamental basis for designing highly efficient bioelectrodes.