关键词: Complexation mechanism Hg(II) ions Selective sorption XPS α-aminophosphonate Complexation mechanism Hg(II) ions Selective sorption XPS α-aminophosphonate Complexation mechanism Hg(II) ions Selective sorption XPS α-aminophosphonate

Mesh : Adsorption Hydrogen-Ion Concentration Kinetics Mercury Spectroscopy, Fourier Transform Infrared Thermodynamics Water Purification / methods

来  源:   DOI:10.1016/j.chemosphere.2022.135253

Abstract:
Herein, efficient and potential chelating α-aminophosphonate based sorbents (AP-) derived from three different amine origins (aniline/anthranilic acid/O-phenylenediamine) to form AP-H, carboxylated and aminated enhanced aminophosphonate as AP-H, AP-COOH, and AP-NH2 were synthesized via a facile method. The structure of the synthesized sorbents was elucidated using different techniques; elemental analysis (CHNP/O), FT-IR, NMR (1H-, 13C and 31P NMR), TGA and BET. The fabricated sorbents were exploited for Hg(II) removal from aqueous solution via sorption properties. Isotherm fitted by Langmuir equation: the maximum sorption capacities at optimum pH 5.5, and T:25 ± 1 °C, were found to be 1.33, 1.23, and 1.15 mmol Hg g-1 for AP-COOH, AP-NH2, AP-H, respectively, which is roughly correlated with the active sites density and the hard/soft characteristics of adsorbents\' reactive groups. Metal-ligand binding affinities are qualitatively rationalized in terms of hard and soft acids and bases (HSAB) theory. The interaction of Hg(II) (soft) has a stronger affinity to AP-COOH can be considered a softer base compared with reference material (AP-H) over than AP-NH2 (hard). This sequence result showed opposite trends consistent with their reciprocal properties according to the steric effect modulates and the specific surface area. Thermodynamics analysis for absolute values of ΔH°, ΔS° and ΔG° afford the selectivity towards Hg(II) sorption with the following order: AP-COOH > AP-NH2 >AP-H. Elution and regeneration was carried out by HCl solution and recycled for a minimum of five cycles, the sorption and desorption efficiencies are greater than 91%. Such sorbents exhibit good durability, stability and promising potential for Hg(II) removal. Finally, a new modelling technique for quantitative non-linear description and comparison of equivalent geographical positions in 3D space of extended relationships. Exothermic and spontaneous behavior were observed using a proposed Floatotherm that included the Van\'t Hoff parameters model.
摘要:
在这里,有效和潜在的螯合α-氨基膦酸酯基吸附剂(AP-)衍生自三种不同的胺来源(苯胺/邻氨基苯甲酸/邻苯二胺)以形成AP-H,作为AP-H的羧化和胺化增强的氨基膦酸酯,AP-COOH,和AP-NH2通过简单的方法合成。使用不同的技术阐明了合成吸附剂的结构;元素分析(CHNP/O),FT-IR,NMR(1H-,13C和31PNMR),TGA和BET。利用制造的吸附剂通过吸附性能从水溶液中去除Hg(II)。由Langmuir方程拟合的等温线:最佳pH5.5和T:25±1°C时的最大吸附容量,发现AP-COOH为1.33、1.23和1.15mmolHgg-1,AP-NH2,AP-H,分别,这大致与活性位点密度和吸附剂反应基团的硬/软特性相关。根据硬酸和软酸和碱(HSAB)理论,金属-配体结合亲和力在质量上是合理的。与参考材料(AP-H)相比,Hg(II)(软)对AP-COOH的相互作用比AP-NH2(硬)具有更强的亲和力,可以认为是更软的碱。根据空间效应调节和比表面积,该序列结果显示了相反的趋势,与它们的倒数性质一致。ΔH°绝对值的热力学分析,ΔS°和ΔG°提供了对Hg(II)吸附的选择性,其顺序如下:AP-COOH>AP-NH2>AP-H。通过HCl溶液进行洗脱和再生,并循环至少五个循环。吸附和解吸效率大于91%。这种吸附剂表现出良好的耐久性,汞(II)去除的稳定性和有希望的潜力。最后,一种新的建模技术,用于定量非线性描述和比较扩展关系的3D空间中的等效地理位置。使用建议的Floatotherm(包括Van\'tHoff参数模型)观察到放热和自发行为。
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