Nanomaterial−Hybridized Biocathodes for Enhanced Hexavalent Chromium Removal and Electricity Generation in Microbial Fuel Cells

To address cathode passivation, performance deterioration, and toxic stress during the removal of hexavalent chromium [Cr(VI)] in biocathode microbial fuel cells (MFCs), this study constructed nanomaterial-hybridized biocathodes to improve electricity generation and Cr(VI) removal in MFCs. Reduced graphene oxide (rGO), nano-iron sulfide (nano-FeS), and rGO/nano-FeS were separately hybridized with biocathodes to systematically investigate the effects of different hybridized biocathodes on the performance of MFCs for Cr(VI)-containing wastewater treatment. The results showed that the FeS group exhibited the best Cr(VI) removal capability, with a maximum removal kinetic constant of 0.184 h−1, which was 3.60 times that of the Control group, and showed the smallest performance decline after three consecutive cycles. Mechanistic analysis indicated that nano-FeS promoted the transformation of Cr(VI) into Cr(III) and Cr(0) through its strong adsorption and reducing capacities; it also enhanced biofilm cell activity and the protein/polysaccharide ratio in extracellular polymeric substances; furthermore, it shaped a multi-taxon-dominated microbial community capable of Cr(VI) tolerance and reduction and enhanced the associated metabolic functions, thereby improving resistance to Cr(VI) stress and effectively alleviating cathode passivation. In contrast, rGO tended to enhance biocathode conductivity and electricity generation in MFCs, with the rGO + FeS group achieving the highest power density output of 51.54 ± 3.62 mW/m2, which was 1.22 times that of the Control group, as well as the smallest decline in power density after three consecutive cycles. Overall, nanomaterial hybridization reshaped interfacial electron transfer and microbial stress resistance in biocathodes, enabling efficient Cr(VI) removal and stable electricity generation, and providing a new strategy to construct long-term stable bioelectrochemical systems for heavy metal-containing wastewater treatment.