More than 80% of wastewater from industries is discharged into receiving water bodies without any pollution control. Microbial fuel cells (MFCs) are a promising technology for the simultaneous treatment of wastewater and electricity production. With regard to azo-dye containing wastewater (e.g., from textile manufacturing), the dye may be fed via the anode chamber containing electrochemically active bacteria or via the cathode chamber containing laccase enzyme as catalyst for oxygen reduction. This study investigated which of the two approaches is the best with regard to rate of decolourization of the dye (Acid orange 7), COD reduction and electricity production. The power density was higher for the MFC Dye Cathode (50 ± 4 mW m −2 , COD reduction 80.4 ± 1.2%) compared with 42.5 ± 2.6 mW m −2 (COD reduction 69 ± 2%) for MFC Dye Anode. The time required for decolourization was longer in the MFC Dye Anode (Shewanella oneidensis) where only 20% decolourization was obtained after 24 h compared to 80% for the MFC Dye Cathode. The anodic dye degradation products were unstable when exposed to air resulting in regaining of color. In case of degradation by laccase in the cathode chamber, the decolourization products were stable and simpler in chemical structure as determined by GC-MS. This work suggests that feeding azo dyes in cathode chambers of MFCs containing laccase is a better way of treating the dyes compared to the commonly used approach of feeding the dye in the anode chamber provided enzyme activity can be sustained.

Enzymatic biocathodes have the potential to replace platinum as an expensive catalyst for the oxygen reduction reaction in microbial fuel cells (MFCs). However, enzymes are fragile and prone to loss of activity with time. This could be circumvented by using suitable immobilization techniques to maintain the activity and increase longevity of the enzyme. In the present study, laccase from Trametes versicolor was immobilized using three different approaches, i.e., crosslinking with electropolymerized polyaniline (PANI), entrapment in copper alginate beads (Cu-Alg), and encapsulation in Nafion micelles (Nafion), in the absence of redox mediators. These laccase systems were employed in cathode chambers of MFCs for decolourization of Acid orange 7 (AO7) dye. The biocatalyst in the anode chamber was Shewanella oneidensis MR-1 in each case. The enzyme in the immobilized states was compared with freely suspended enzyme with respect to dye decolourization at the cathode, enzyme activity retention, power production, and reusability. PANI laccase showed the highest stability and activity, producing a power density of 38 ± 1.7 mW m−2 compared to 25.6 ± 2.1 mW m−2 for Nafion laccase, 14.7 ± 1.04 mW m−2 for Cu-Alg laccase, and 28 ± 0.98 mW m−2 for the freely suspended enzyme. There was 81% enzyme activity retained after 1 cycle (5 days) for PANI laccase compared to 69% for Nafion and 61.5% activity for Cu-alginate laccase and 23.8% activity retention for the freely suspended laccase compared to initial activity. The dye decolourization was highest for freely suspended enzyme with over 85% decolourization whereas for PANI it was 75.6%, Nafion 73%, and 81% Cu-alginate systems, respectively. All the immobilized laccase systems were reusable for two more cycles. The current study explores the potential of laccase immobilized biocathode for dye decolourization in a microbial fuel cell.

Summary Microbial biocathodes are gaining interest due to their low cost, environmental friendliness and sustainable nature. In this study, a microbial consortium was enriched from activated sludge obtained from a common textile effluent treatment plant in the absence of organic carbon source to produce an electroactive biofilm. Chronoamperometry method of enrichment was carried out for over 70 days to select for electroactive bacteria that could be used as a cathode catalyst in microbial fuel cells (MFC). The resultant biofilm produced an average peak current of −0.7 mA during the enrichment and produced a maximum power density of 64.6 ± 3.5 mW m−2 compared to platinum (72.7 ± 1.2 mW m−2) in a Shewanella‐based MFC. Microbial community analysis of the initial sludge sample and enriched samples, based on 16S rRNA gene sequencing, revealed the selection of chemolithotrophs with the most dominant phylum being Bacteroidetes, Proteobacteria, Firmicutes, Actinobacteria and Acidobacteria in the enriched samples. A variety of CO2 fixing and nitrate‐reducing bacteria was present in the resultant biofilm on the cathode. This study suggests that microbial consortia are capable of replacing expensive platinum as a cathode catalyst in MFCs.

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