4.7 Article

Utilization of gel-type polystyrene host for immobilization of nano-sized hydrated zirconium oxides: A new strategy for enhanced phosphate removal

Journal

CHEMOSPHERE
Volume 263, Issue -, Pages -

Publisher

PERGAMON-ELSEVIER SCIENCE LTD
DOI: 10.1016/j.chemosphere.2020.127938

Keywords

Phosphate; Adsorption; Gel-type polymer; Nanocomposite; Zirconium oxides

Funding

  1. National Natural Science Fund [51708280/51761165011]
  2. National Water Pollution Control and Treatment Science and Technology Major Project [2017ZX07204001]
  3. National Key Research and Development Program of China [2016YFA0203104/2017YFE0107200]

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The study developed a new strategy to enhance phosphate adsorptive removal by immobilizing zirconium oxides nanoparticles onto a gel-type anion exchange resin, denoted as HZO@N201, which exhibited superior phosphate adsorptive capacity and affinity towards phosphate compared to HZO@D201. The results showed that HZO@N201 had smaller particle size and richer surface hydroxyl groups, facilitating phosphate diffusion and inner-sphere complexes formation, leading to enhanced reactivity and effective treatable volume in fixed-bed runs. The gel-type polymeric host was believed to promote the dispersion of smaller nanoparticles and expose more surface hydroxyl groups, offering insights to a new strategy for immobilization of functional nanoparticles for enhanced phosphate removal.
The urgent need for eutrophication control motivated the development of many novel adsorbents for enhanced phosphate polishing removal. Among these, zirconium-based nanomaterial was regarded as an effective kind because of its ability to bind phosphate specifically via inner-sphere complexation. In this study, we proposed a new strategy to improve the efficiency of zirconium oxides (HZO) nanoparticles by immobilizing them onto a gel-type anion exchange resin covalently attached with ammonium groups, denoted as HZO@N201. A previously developed macro-porous polymeric nanocomposite HZO@D201 was used for comparison. The immobilized nanoparticles in HZO@N201 were well dispersed in the gel matrix, manifesting smaller particle size and richer surface hydroxyl groups in comparison to HZO@D201. As a result of the structural merits in collective, HZO@N201 not only exhibited superior phosphate adsorptive capacity and affinity towards phosphate to HZO@D201, but also facilitate phosphate diffusion, based on isotherm, pH and kinetic tests. Mechanistic study by XPS and 31P SS-NMR substantiated the selective phosphate adsorption pathway as the formation of inner-sphere complexes by HZO@N201, which exhibited enhanced reactivity than HZO@D201. Lastly, fixed-bed runs of HZO@N201 was conducted, achieving an effective treatable volume of 2000 BV, which was 600 BV more than HZO@D201. Additional adsorption-regeneration cycle confirmed its reusability and potential for practical application. We believe the gel-type polymeric host could facilitate the formation and dispersion of smaller sized nanoparticles, exposing more surface hydroxyl groups highly accessible to phosphate. The results of this paper offer insights to a new strategy for immobilization of functional nanoparticles aiming at enhanced adsorptive removal of phosphate. (C) 2020 Elsevier Ltd. All rights reserved.

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