Selective butyrate production from CO₂ and methanol in microbial electrosynthesis - influence of pH

Methanol assisted microbial electrosynthesis (MES) enables butyrate production from carbon dioxide and methanol using external electricity. However, the effects of operational parameters on butyrate formation remain unclear. By running three flat plate MES reactors with fed-batch mode at three controlled pH values (5.5, 6 and 7), the present study investigated the influence of pH on methanol assisted MES by comparing the process performance, microbial community structure, and genetic potential. The highest butyrate selectivity (87 % on carbon basis) and the highest butyrate production rate of 0.3 g L^-1 d^-1 were obtained at pH 6. At pH 7, a comparable butyrate production rate was achieved, yet with a lower selectivity (70 %) accompanied with acetate production. Butyrate production rate was considerably hindered at pH 5.5, reaching 0.1 g L^-1 d^-1, while the selectivity reached was up to 81 %. Methanol and CO₂ consumption increased with pH, along with more negative cathodic potential and more negative redox potential. Furthermore, pH affected the thermodynamical feasibility of involved reactions. The results of metagenomic analyses suggest that Eubacterium callanderi dominated the microbial communities at all pH values, which was responsible for methanol and CO₂ assimilation via the Wood-Ljungdahl pathway and was likely the main butyrate producer via the reverse β-oxidation pathway.