Biochar-assisted water electrolysis (BAWE) has the potential to reduce the electricity consumption of hydrogen production. However, prolonged electrolysis leads to over-oxidation of biochar, reduced reactivity, and decreasing hydrogen production at cathode. Herein, we proposed the electrochemical activation of biochar via limited biochar oxidation reaction (BOR) and hydrogen evolution reaction (HER) in BAWE process, and the upgraded biochar was employed to remove Cr(VI). Distinct biochar was first pyrolyzed from three kinds of representative biomass components, cellulose, lignin, and their mixture at different temperatures. All of them exhibited excellent BOR activity, especially the biochar derived by the pyrolyzed cellulose and lignin at 800 degrees C (MBC-800) required a potential as low as 1.319 V vs. RHE@1 mA cm(-2) using Pt electrode in 1 M KOH and achieved a Faraday efficiency almost 100% for hydrogen production. BAWE presented an energy-saving electrical consumption of 4.98 kWh Nm(-3) H-2 compared to the conventional water electrolysis of 5.32 kWh Nm(-3) H-2. Electrochemical oxidation enriched the oxygen-containing groups on biochar surface, which significantly improved its reductivity towards Cr(VI) and complexation with Cr(III), leading to the removal rate of Cr(VI) more than doubled. Results showed the achievement of electrochemical activation of biochar by limited electrooxidation. These findings provide a new route for the high-value utilization of biochar and energy-saving electrolytic hydrogen production.
