Xinhong Qiu

Mechanism of boron uptake by hydrocalumite calcined at different temperatures

Hydrocalumite (Ca-Al-layered double hydroxide (LDH)) was prepared and applied for the removal of borate. The properties of Ca-Al-LDH calcined at different temperatures were diverse, which affected the sorption density and mechanism of boron species. The sorption density increased with increase in calcined temperature and the sample calcined at 900°C (Ca-Al-LDH-900) showed the maximum sorption density in this work. The solid residues after sorption were characterized by (11)B NMR, (27)Al NMR, SEM, and XRD to investigate the sorption mechanism. Dissolution-reprecipitation was the main mechanism for sorption of borate in Ca-Al-LDH. For Ca-Al-LDH calcined at 300 and 500°C, regeneration occurred in a short time and the newly forming LDHs were decomposed to release Ca(2+) ions and formed ettringite with borate. Two stages occurred in the sorption of boron by Ca-Al-LDH calcined at 900°C. In the first stage, boron species adsorbed on the alumina gel resulting from the hydration of calcined products. In this stage, borate was included as an interlayer anion into the newly forming LDHs in the following stage, and then immobilized as HBO3(2-) into the interlayer, most the LDHs.

Sorption of H3BO3/B(OH)4− on calcined LDHs including different divalent metals

LDHs with different divalent metals (Zn-LDH, Mg-LDH and Ca-LDH) have been synthesized and produced calcined LDHs (Zn-CLDH, Mg-CLDH and Ca-CLDH) for borate removal. Based on XRD, SEM, BET, (27)Al NMR, CO2-TPD, and (11)B NMR, detailed characterization of different CLDHs before and after reaction with the boron species was systematically performed. The surface area, basicity and the particle charge of the different CLDHs, which are related to the hydration and regeneration, were markably influenced by the nature of the divalent metals. Transformation of crystal phases and the types of boron species adsorbed by the different CLDHs varied as time changed. The regeneration of Ca-CLDH required the shortest time. However, Ca-LDH decomposed to release Ca(2+) ions, forming ettringite with borate. Zn-CLDH also rapidly transformed into Zn-LDH. During this reconstruction, B(OH)4(-) was intercalated into the interlayer of Zn-LDHs, which is the predominant mechanism of borate removal by Zn-CLDH. Increase in the initial pH caused a competition between borate and OH(-) so that the removal efficiency of borate by Zn-CLDH decreased. For Mg-CLDH, surface complexation and electrostatic attraction were included in the first stage, immobilizing boric acid into Mg(OH)2 and attracting borate as interlayer anionic species into the new forming Mg-LDHs in the second stage.

Structural Memory Effect of Mg–Al and Zn–Al layered Double Hydroxides in the Presence of Different Natural Humic Acids: Process and Mechanism

The structural memory effect of layered double hydroxides (LDHs) is one of the important reasons for their extensive use in environmental remediation. In this study, humic acid (HA) was extracted from black soil and sediments and characterized to determine their structures. The regeneration mechanisms of calcinated LDHs (CLDHs) including different divalent metals (Mg-CLDH and Zn-CLDH) in deionized water and different HA solutions were carefully elucidated, and the reasons for the behavior differences in the two materials were explained. The presence of the HAs significantly increased the dissolution rate of Mg2+ ions from Mg-CLDHs and subsequent regeneration of Mg-LDH. Because of the diverse functional groups in the HAs, these groups were complexed with metallic ions such as Mg2+ on the surface of Mg-CLDH in the beginning. During the process, the HAs adsorbed the regenerated LDHs on the surfaces. Therefore, the crystallinity, morphology, and specific surface area of the regenerated Mg-LDH significantly changed, especially in the presence of high concentrations of HA. In the case of Zn-CLDH, the regeneration rate of the LDH increased in the presence of HA, but the surface of Zn-CLDH was covered with regenerated Zn-LDH and HA. Then, the inside of the particles could not transform to LDH, leading to poor crystallinity and a significant increase in the ZnO content of the HA system.