Bioelectrochemical systems (BESs) are unique systems capable of converting the chemical energy of organic waste including low-strength wastewaters and lignocellulosic biomass into electricity or hydrogen/chemical products in microbial fuel cells (MFCs) or microbial electrolysis cells (MECs) respectively, or other products formed at the cathode by an electrochemical reduction process. As compared to conventional fuel cells, BESs operate under relatively mild conditions, use a wide variety of organic substrates and mostly do not use expensive precious metals as catalysts. The recently discovered use of BES for product synthesis via microbial electrosynthesis have greatly expanded the horizon for these systems. Newer concepts in application as well as development of alternative materials for electrodes, separators, and catalysts, along with innovative designs have made BESs very promising technologies. This article discusses the recent developments that have been made in BESs so far, with an emphasis on their various applications beyond electricity generation, resulting performances and current limitations.

Different electrolytes applied in the aqueous electrocatalytic CO2 reduction reaction (CO2RR) considerably influence the catalyst performance. Their concentration, species, buffer capacity, and pH value influence the local reaction conditions and impact the product distribution of the electrocatalyst. Relevant properties of prospective solvents include their basicity, CO2 solubility, conductivity, and toxicity, which affect the CO2RR and the applicability of the solvents. The complexity of an electrochemical system impedes the direct correlation between a single parameter and cell performance indicators such as the Faradaic efficiency; thus the effects of different electrolytes are often not fully comprehended. For an industrial application, a deeper understanding of the effects described in this review can help with the prediction of performance, as well as the development of scalable electrolyzers. In this review, the application of supporting electrolytes and different solvents in the CO2RR reported in the literature are summarized and discussed.