Pyrolysis temperature affects the physiochemical characteristics of lanthanum-modified biochar derived from orange peels: Insights into the mechanisms of tetracycline adsorption by spectroscopic analysis and theoretical calculations

Abstract

Biochar (BC) derived from orange peels was modified using LaCl₃ to enhance its tetracycline (TC) adsorption capacity. SEM-EDS, FT-IR, XRD, and BET were used to characterize the physiochemical characteristics of La-modified biochar (La-BC). Batch experiments were conducted to investigate the effects of several variables like pyrolysis temperature, adsorbent dosage, initial pH, and coexisting ions on the adsorption of TC by La-BC. XPS and density functional theory (DFT) were used to elucidate the TC adsorption mechanism of La-BC. The results demonstrated that La was uniformly coated on the surface of the La-BC. The physiochemical characteristics of La-BC highly depended on pyrolysis temperature. Higher temperature increased the specific surface area and functional groups of La-BC, thus enhancing its TC adsorption capacity. La-BC prepared at 700 °C (BC@La-700) achieved the maximum adsorption capacity of 143.20 mg/g, which was 6.8 and 4.6 times higher than that of BC@La-500 and BC@La-600, respectively. The mechanisms of TC adsorption by La-BC were most accurately described by the pseudo-second-order kinetic model. Furthermore, the adsorption isotherm of La-BC was consistent with the Freundlich model. BC@La-700 achieved good TC adsorption efficiencies even at a wide pH range (pH 4-10). Humic acid significantly inhibited TC adsorption by La-BC. The presence of coexisting ions (NH₄⁺, Ca²⁺, NO₃^-) did not significantly affect the adsorption capacity of La-BC, particularly BC@La-700. Moreover, BC@La-700 also exhibited the best recycling performance, which achieved relative high adsorption capacity even after 5 cycles. The XPS results showed that π-π bonds, oxygen-containing functional groups, and La played a major role in the adsorption of TC on La-BC. The result of DFT showed that the adsorption energy of La-BC was the greatest than that of other functional groups on biochar. Collectively, our findings provide a theoretical basis for the development of La-BC based materials to remove TC from wastewater.

Keywords: Adsorption isotherm; Biochar; Density functional theory; La modification; Tetracycline.