Characterization of graphene/pine wood biochar hybrids: Potential to remove aqueous Cu²

Biochar-based hybrid composites containing added nano-sized phases are emerging adsorbents. Biochar, when functionalized with nanomaterials, can enhance pollutant removal when both the nanophase and the biochar surface act as adsorbents. Three different pine wood wastes (particle size < 0.5 mm, 10 g) were preblended with 1 wt% of three different graphenes in aqueous suspensions, designated as G1, G2, and G3. G1 (S_BET, 8.1 m²/g) was prepared by sonicating graphite made from commercial synthetic graphite powder (particle size 7-11 μm). G2 (312.0 m²/g) and G3 (712.0 m²/g) were purchased commercial graphene nanoplatelets (100 mg in 100 mL deionized water). These three pine wood-graphene mixtures were pyrolyzed at 600 °C for 1 h to generate three graphene-biochar adsorbents, GPBC-1, GPBC-2, and GPBC-3 containing 4.4, 4.9, and 5.0 wt% of G1, G2, and G3 respectively. Aqueous Cu²⁺ adsorption capacities were 10.6 mg/g (GPBC-1), 4.7 mg/g (GPBC-2), and 5.5 mg/g (GPBC-3) versus 7.2 mg/g for raw pine wood biochar (PBC) (0.05 g adsorbent dose, Cu²⁺ 75 mg/L, 25 mL, pH 6, 24 h, 25 ± 0.5 °C). Increased graphene surface areas did not result in adsorption increases. GPBC-1, containing the lowest nanophase surface area with the highest Cu²⁺ capacity, was chosen to evaluate its Cu²⁺ adsorption characteristics further. Results from XPS showed that the surface concentration of oxygenated functional groups on the GPBC-1 is greater than that on the PBC, possibly contributing to its greater Cu²⁺ removal versus PBC. GPBC-1 and PBC uptake of Cu²⁺ followed the pseudo-second-order kinetic model. Langmuir maximum adsorption capacities and BET surface areas were 18.4 mg/g, 484.0 m²/g (GPBC-1) and 9.2 mg/g, 378.0 m²/g (PBC). This corresponds to 3.8 × 10^-2 versus 2.4 × 10^-2 mg/m² of Cu²⁺ removed on GPBC-1 (58% more Cu²⁺ per m²) versus PBC. Cu²⁺ adsorption on both these adsorbents was spontaneous and endothermic.