Correlating electrochemical biochar oxidation with electrolytes during biochar-assisted water electrolysis for hydrogen production

Biochar-assisted water electrolysis (BAWE) for hydrogen production is employed to reduce energy consumption by replacing the oxygen evolution reaction (OER) with thermodynamically more favorable biochar oxidation reaction (BOR). Electrolyte, as a carrier to dissolve the biochar particles and form conductive solution, is essential for the transfer and transformation of biochar particles and free radical precursors. Herein, the effects of electrolyte type, concentration, and pH on the BOR performance of BAWE system were investigated. Results show that 1 M KOH solution as an electrolyte was more suitable for the BAWE system, and the BOR of the alkaline BAWE system had the higher electrochemical activity (E10 = 1.649 V vs RHE, 56 mV∙dec−1) compared with the OER in conventional water electrolysis system (E10 = 1.982 V vs RHE, 189 mV∙dec−1). The anion adsorption phenomenon appeared in acidic media restricted the BOR kinetics. In addition, the diffusion coefficient of anodic reaction components showed a first decrease and then increase trend when the pH increased. And the diffusion coefficient reached the maximum value of 3.11 × 10−3 cm2∙s−1 at pH of 13.98, which was favorable for accelerating the diffusion of reaction components from the bulk solution to the electrode surface. This work can provide guidance for further improving the diffusion of reaction components, the biochar oxidation rate and hydrogen production in BAWE process.