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.

Biochar (BC) derived from orange peels was modified using LaCl 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 (NH, Ca, NO) 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.