Ball-milled biochars (BM-biochars) were produced through ball milling of pristine biochars derived from different biomass at three pyrolysis temperatures (300, 450, and 600 °C). The results of scanning electron microscopic (SEM), surface area, hydrodynamic diameter test, and Fourier transform infrared spectroscopy (FTIR) revealed that BM-biochars had smaller particle size (140-250 nm compared to 0.5-1 mm for unmilled biochar), greater stability, and more oxygen-containing functional groups (2.2-4.4 mmol/g compared to 0.8-2.9 for unmilled biochar) than the pristine biochars. With these changes, all the BM-biochar-modified glassy carbon electrodes (BM-biochar/GCEs) exhibited prominent electrochemical properties (e.g., ΔEp of 119-254 mV compared to 850 mV for bare GCE). Cyclic voltammetry (CV) and electrochemical impedance spectra (EIS) show that ball-milled 600 °C biochar/GCE (BMBB600/GCE and BMBG600/GCE) had the smallest peak-to-peak separation (ΔEp = 119 and 132 mV, respectively), series resistance (RS = 88.7 and 89.5 Ω, respectively), and charge transfer resistance (RCT = 1224 and 1382 Ω, respectively), implying its best electrocatalytic activity for the reduction of Fe(CN)63-. It is supposed that the special structure (i.e., internal surface area, pore volume, oxygen-containing functional groups, and graphitic structure) facilitates the electron transfer and reduces interface resistance. Economic cost of BM-biochar/GCE was 1.97 × 10-7 USD/cm2, much lower than that of a "low-cost platinum electrode" (0.03 USD/cm2). The results indicate potential application of the novel BM-biochar for low cost and high efficient electrodes. Graphical abstract.
Keywords: Ball-milled biochar; Electrode; Mechanisms; Oxygen-containing functional groups; Surface area.