Comparative Study on the Performance and Mechanism of Adsorption–Oriented Phosphorus–Modified High–Efficiency and Durable Activated Biochar from Fast Pyrolysis

Abstract

Extensive research has demonstrated the advantageous utilization of medium–low temperature fast pyrolysis (FP) for biomass, yielding high–grade liquid–phase chemicals or fuels. However, the field of FP–based high–performance solid biochar research still presents several gaps. Herein, a one–step versus two–step method for biomass H3PO4 activation under FP was comparatively analyzed for the first time, and efficiently activated carbons (ACs) for dye removal were successfully synthesized at a low temperature (723 K). Investigation of methylene blue (MB) adsorption revealed that the one–step sample P–H–0.5, possessing a specific surface area of 1004 m2·g−1, exhibited a remarkable adsorption capacity of 695.54 mg·g−1 with an ultra–high removal rate (99.94%, C0 = 150 mg·L−1). The two–step sample P–2–H–2, a modified byproduct of FP, achieved efficient dye adsorption in the shortest time (2 min, 383.91 mg·g−1). This originated from the well–developed surface macropores and elevated group content derived from phosphorus (P)—modification. Both adsorption data were well–fitted with pseudo–second–order kinetics and the Langmuir model, revealing the presence of chemical effects and the dominance of monolayer adsorption. A more detailed kinetic study suggested intrapore transport primarily governed the adsorption process on P–H–0.5, whereas P–2–H–2 relied on surface diffusion. FTIR and XPS revealed notable differences in the active sites between the two methods. Aside from –OH, –COOH with C–O–P, the P elements of P–H–0.5 were classified as C–P–O3 and C2–O–P2, demonstrating the ability of one–step FP to introduce heteroatoms into carbon defects. The basic interactions of ACs with MB were π–π stacking and hydrogen bonding established by –OH–containing groups. At a suitable pH (>5), most H+ was removed from the surface, and the electrostatic attraction became the strongest linking force. Both ACs exhibited exceptional reusability, with removal rates surpassing 90% of the initial rate after four cycles of regeneration.