We developed a technique based on the use of microsensors to measure pH and H₂ gradients during microbial electrosynthesis. The use of 3D electrodes in (bio)electrochemical systems likely results in the occurrence of gradients from the bulk conditions into the electrode. Since these gradients, e.g., with respect to pH and reactant/product concentrations determine the performance of the electrode, it is essential to be able to accurately measure them. Apart from these parameters, also local oxidation-reduction potential and electric field potential were determined in the electrolyte and throughout the 3D porous electrodes. Key was the realization that the presence of an electric field disturbed the measurements obtained by the potentiometric type of microsensor. To overcome the interference on the pH measure, a method was validated where the signal was corrected for the local electric field measured with the electric potential microsensor. The developed method provides a useful tool for studies about electrode design, reactor engineering, measuring gradients in electroactive biofilms, and flow dynamics in and around 3D porous electrodes of (bio)electrochemical systems.

Microbial electrosynthesis is an uprising concept for the combined carbon dioxide reduction and electricity storage in the form of green chemical compounds. Although several proof of principle studies show great promise, mass-transfer limitations of substrates, protons and products remains one of the issues that needs to be addressed to bring the systems towards greater scale applications. A previously tested solution formed force flow-through catholyte recirculation, but this set-up encountered difficulties with gas accumulation during start-up at higher current densities (∼ −10 kA/m ³), creating the need for a bypass to release gas. In this study, start-up at high current density was achieved without a bypass by using an alternating flow-through regime. This regime decreased the operating energy input from 221 to 136 kWh per kg of produced hydrogen and reached acetate production within 10 days after start-up at high current density and elongation to n-caproate after 45 days. Mass-transfer studies were included by microsensor measurements of local conditions (hydrogen concentration, pH) combined with thermodynamic calculations at the start and end of 60-days biotic experiments. The microorganisms on the cathode decreased pH gradients and consumed the formed hydrogen. The presence of Clostridium sensu stricto 12 and Peptococcaceae species were related to chain elongation activity, and the presence of Methanobrevibacter was linked to methanogenesis activity. By identifying the effects of different flow-through strategies on local concentrations and functional microbial groups, this work provides insights on the optimal conditions for microbial CO ₂ conversion and highlight the application potential of microbial electrosynthesis.