| Summary: | Microbial fuel cells (MFCs) provide considerable benefits in the energy and environmental sectors for producing bioenergy during bioremediation. Recently, new hybrid composite membranes with inorganic additives have been considered for MFC application to replace the high cost of commercial membranes and improve the performances of cost-effective polymers, such as MFC membranes. The homogeneous impregnation of inorganic additives in the polymer matrix effectively enhances the physicochemical, thermal, and mechanical stabilities and prevents the crossover of substrate and oxygen through polymer membranes. However, the typical incorporation of inorganic additives in the membrane decreases the proton conductivity and ion exchange capacity. In this critical review, we systematically explained the impact of sulfonated inorganic additives (such as (sulfonated) sSiO<sub>2</sub>, sTiO<sub>2</sub>, sFe<sub>3</sub>O<sub>4</sub>, and s-graphene oxide) on different kinds of hybrid polymers (such as PFSA, PVDF, SPEEK, SPAEK, SSEBS, and PBI) membrane for MFC applications. The membrane mechanism and interaction between the polymers and sulfonated inorganic additives are explained. The impact of sulfonated inorganic additives on polymer membranes is highlighted based on the physicochemical, mechanical, and MFC performances. The core understandings in this review can provide vital direction for future development.
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