Highly Efficient Water Decontamination by Using Sub-10 nm FeOOH Confined within Millimeter-Sized Mesoporous Polystyrene Beads.

Millimeter-sized polymer-based FeOOH nanoparticles (NPs) provide a promising option to overcome the bottlenecks of direct use of NPs in scaled-up water purification, and decreasing the NP size below 10 nm is expected to improve the decontamination efficiency of the polymeric nanocomposites due to the size and surface effect. However, it is still challenging to control the dwelled FeOOH NP sizes to sub-10 nm, mainly due to the wide pore size distribution of the currently available polymeric hosts. Herein, we synthesized mesoporous polystyrene beads (MesoPS) via flash freezing to assemble FeOOH NPs. The embedded NPs feature with α-crystal form, tunable size ranging from 7.3 to 2.0 nm and narrow size distribution. Adsorption of As(III/V) by the resultant nanocomposites was greatly enhanced over the α-FeOOH NPs of 18 × 60 nm, with the iron mass normalized capacity of As(V) increasing to 10.3 to 14.8 fold over the bulky NPs. Higher density of the surface hydroxyl groups of the embedded NPs as well as their stronger affinity toward As(V) was proved to contribute to such favorable effect. Additionally, the as-obtained nanocomposites could be efficiently regenerated for cyclic runs. We believe this study will shed new light on how to fabricate highly efficient nanocomposites for water decontamination.

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

Enhanced Arsenite Removal from Silicate-containing Water by Using Redox Polymer-based Fe(III) Oxides Nanocomposite.

The efficient removal of arsenite [As(III)] from groundwater remains a great challenge. Nanoscale oxides of Fe(III), Zr(IV), and Al(III) can selectively remove arsenic from groundwater through inner-sphere complexation. However, owing to polysilicate coatings formation on nanoparticles surface, the ubiquitous silicate exerts remarkably adverse effects on As(III) removal. Herein, we propose a new strategy to enhance silicate resistance of nanoscale oxides by embedding them inside the redox polymer host. As a proof-of-concept, the nanocomposite HFO@PS-Cl was employed to remove As(III) from silicate-containing water. The polymer host (PS-Cl) contains active chlorine to oxidize As(III) into arsenate [As(V)], and the embedded Fe(III) oxides enabling specific adsorption toward arsenic. Silicate exerts negligible effects on As(III) removal by HFO@PS-Cl in pH 3-7, but increasing the residual arsenic concentration from 49 µg/L to 166 µg/L for the solutions treated by HFO@PS-N, i.e., the nanoscale Fe(III) oxides embedded inside the polymer host without active chlorine. During the six cyclic decontamination-regeneration assays, HFO@PS-Cl steadily reduces As(III) below 10 µg/L. As for HFO@PS-N, however, the residual arsenic increases to ~57 µg/L in the sixth run. In column mode, HFO@PS-Cl column generates >3200-bed volume (BV) clean water ([As]<10 µg/L) from the simulated As(III)-contaminated groundwater. In contrast, the values for As(V)-contaminated water and HFO@PS-N column are only ~650 BV and ~608 BV, respectively. The stoichiometric assays, XPS, and in-situ ATR-FTIR analysis demonstrate that silicate polymerization is intensively suppressed by the protons produced during As(III) oxidation, thus rendering HFO@PS-Cl with excellent silicate resistant properties.