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[Display omitted] • Specific colonization pattern of key symbionts in MES was firstly investigated. • Co-colonization of EAB and CSB promoted caproate biosynthesis in MES. • CSB and EAB mutually interacted in metabolic activity and enhanced electron transfer. • Ecological mechanism was revealed in terms of MEN analysis and Mantel test. • Economic benefit and carbon emission were preferable via co-colonization. As promising and value-added platform chemicals, the biosynthesis of medium-chain fatty acids (MCFAs, C6-C12) via chain elongation (CE) in microbial electrosynthesis systems (MES) has recently garnered significant attentions due to the unique bioelectrocatalytic behaviors and the reduction of exogenous electron donors (EDs). Caproate-synthesizing bacteria (CSB) played a crucial role in the generation of acetyl-CoA, which subsequently underwent reverse β oxidation to synthesize MCFAs. However, the presence of electrochemically active bacteria (EAB) was also pivotal for MES as they generated hydrogen in the cathodic electron transfer pathways, the specific colonization patterns of key symbionts remained unknown. The aim of this study was to investigate the selective colonization of EAB and CSB on the performance of caproate production in MES. The reactors colonized EAB and CSB achieved the maximum caproate concentration of 5332.5 mg COD/L, which was 7.9 and 1.3 times higher compared to that inoculated with either sole EAB or CSB, respectively. Moreover, the reactors colonized with mixed culture exhibited a clear redox peak and preferable electron transfer efficiency. CSB and EAB mutually interacted in metabolic activities, thereby resulting in increased substrate utilization and caproate production. The findings of this study provide a new strategy and insights for value-added chemicals recovery in microbial electrosynthesis platform. [ABSTRACT FROM AUTHOR]

Bioelectrochemical systems were proposed as a promising approach for the efficient valorization of biomass into 6–8 carbon atom medium-chain fatty acids (MCFAs), the precursors for high value-added chemicals or renewable energy, via acetyl-CoA-mediated chain elongation (CE). To achieve CE processes, exogenous electron donors (EDs), e.g., ethanol or lactic acid, were normally prerequisites. This research built a microbial electrolysis cell (MEC) for MCFAs biosynthesis from acetate without exogenous EDs addition. A wide range of applied voltages (0.6–1.2 V) was first employed to investigate the bioelectrocatalyzing response. The results show that caproate and butyrate were the main products formed from acetate under different applied voltages. Maximum caproate concentration (501 ± 12 mg COD/L) was reached at 0.8 V on day 3. Under this applied voltage, hydrogen partial pressure stabilized at about 0.1 bar, beneficial for MCFA production. Electron and carbon balances revealed that the electron-accepting capacity achieved 32% at 0.8 V, showing the highest interspecies electron transfer efficiency. Most of the carbon was recovered in the form of caproate (carbon loss was 9%). MiSeq sequencing revealed Rhodobacter and Clostridium_sensu_stricto playing the crucial role in the biosynthesis of caproate, while Acetobacterium , Acetoanaerobium , and Acetobacter represented the main ED contributors. Four available flora, i.e., homo-acetogen, anaerobic fermentation bacteria, electrode active bacteria, and nitrate-reducing bacteria, interacted and promoted caproate synthesis by molecular ecological network analysis. [Display omitted] • Optimal applied voltages for caproate production in MECs was firstly elucidated. • Hydrogen/ethanol in situ generated served as EDs without exogenous EDs addition. • Electron acceptability, carbon balance and hydrogen partial pressure were analyzed. • Caproate concentration and specificity achieved maximum under 0.8 V. • Synergistic and competitive interactions among functional microflora were revealed. [ABSTRACT FROM AUTHOR]