The
tandem application of CO2 electrolysis with syngas
fermentation holds promise for achieving heightened production rates
and improved product quality. However, the significant impact of syngas
composition on mixed culture-based microbial chain elongation remains
unclear. Additionally, effective methods for generating syngas with
an adjustable composition from acidic CO2 electrolysis
are currently lacking. This study successfully demonstrated the production
of medium-chain fatty acids from CO2 through tandem acidic
electrolysis with syngas fermentation. CO could serve as the sole
energy source or as the electron donor (when cofed with acetate) for
caproate generation. Furthermore, the results of gas diffusion electrode
structure engineering highlighted that the use of carbon black, either
alone or in combination with graphite, enabled consistent syngas generation
with an adjustable composition from acidic CO2 electrolysis
(pH 1). The carbon black layer significantly improved the CO selectivity,
increasing from 0% to 43.5% (0.05 M K+) and further to
92.4% (0.5 M K+). This enhancement in performance was attributed
to the promotion of K+ accumulation, stabilizing catalytically
active sites, rather than creating a localized alkaline environment
for CO2-to-CO conversion. This research contributes to
the advancement of hybrid technology for sustainable CO2 reduction and chemical production.