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聚苯乙烯阴离子交换剂负载水合氧化铁纳米复合材料对水中钼酸盐的选择性吸附

Selective adsorption of molybdate from water by polystyrene anion exchanger-supporting nanocomposite of hydrous ferric oxides.

作者信息

Li Jiafeng, Chen Du, Liao Xue, Pan Bingjun

机构信息

College of Environment, Zhejiang University of Technology, Hangzhou, Zhejiang 310032, China.

College of Environment, Zhejiang University of Technology, Hangzhou, Zhejiang 310032, China.

出版信息

Sci Total Environ. 2019 Nov 15;691:64-70. doi: 10.1016/j.scitotenv.2019.07.109. Epub 2019 Jul 9.

Abstract

Molybdenum is an essential trace element for humans but can be harmful with excess assimilations or chronic exposures. In this study a polymer-functionalized nanocomposite (HFO-PsAX) was fabricated for selective adsorption of molybdate from aqueous solution. HFO-PsAX was prepared by grafting hydrous ferric oxide nanoparticles (HFOs) into the porous structure of a polystyrene anion exchanger (PsAX) by in situ synthesis method. The resultant HFO-PsAX exhibited greatly enhanced selectivity toward molybdate as compared with the matrix, PsAX, which is also a fair adsorbent for scavenging molybdate. The competitive abilities of the ubiquitous anions, i.e., chloride, carbonate, sulfate, and phosphate, on the adsorption of molybdate by HFO-PsAX followed the order: chloride < phosphate < carbonate < sulfate. The unexpectedly weak competitive ability of trivalent phosphate may be due to incompletely dissociated state and formation of molybdate-phosphate complexes. The optimal pH for the adsorption of molybdate was determined as pH≈4, which is associated with the dissociation constants of molybdic acid; certain adsorption capacities were also observed even under extremely alkaline condition (pH=14) for single-component molybdate solution. Temperature (10, 25, and 40°C) has negligible effect on the adsorption capacities by HFO-PsAX, and Freundlich model and Dubinin-Radushkevich (D-R), Temkin model can describe the adsorption isotherms well. The adsorption potential of Temkin model is calculated as ≈100J/mol, which is between those of physisorption and chemisorption process. Fixed-bed column adsorption experiments validated the potential of HFO-PsAX in treating Mo(VI) contaminated water for practical application, and the exhausted HFO-PsAX can be regenerated by a binary NaOH-NaCl solution (both 5% in mass) without loss in adsorption capacities.

摘要

钼是人体必需的微量元素,但过量摄入或长期接触可能有害。在本研究中,制备了一种聚合物功能化纳米复合材料(HFO-PsAX),用于从水溶液中选择性吸附钼酸盐。通过原位合成法将水合氧化铁纳米颗粒(HFOs)接枝到聚苯乙烯阴离子交换剂(PsAX)的多孔结构中制备了HFO-PsAX。与基质PsAX相比,所得的HFO-PsAX对钼酸盐的选择性大大提高,PsAX也是一种用于清除钼酸盐的良好吸附剂。常见阴离子即氯离子、碳酸根离子、硫酸根离子和磷酸根离子对HFO-PsAX吸附钼酸盐的竞争能力顺序为:氯离子<磷酸根离子<碳酸根离子<硫酸根离子。三价磷酸根离子出人意料的弱竞争能力可能是由于其不完全解离状态以及钼酸盐-磷酸盐络合物的形成。确定吸附钼酸盐的最佳pH值为pH≈4,这与钼酸的解离常数有关;即使在极碱性条件(pH=14)下,对于单组分钼酸盐溶液也观察到一定的吸附容量。温度(1°C、25°C和40°C)对HFO-PsAX的吸附容量影响可忽略不计,Freundlich模型以及Dubinin-Radushkevich(D-R)、Temkin模型能够很好地描述吸附等温线。Temkin模型的吸附势计算为≈100J/mol,介于物理吸附和化学吸附过程之间。固定床柱吸附实验验证了HFO-PsAX在实际应用中处理钼(VI)污染水的潜力,耗尽的HFO-PsAX可用二元NaOH-NaCl溶液(质量分数均为5%)再生,且吸附容量无损失。

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