Chao Shan

Enhanced Phosphate Removal by Nanosized Hydrated La(III) Oxide Confined in Cross-linked Polystyrene Networks

A new nanocomposite adsorbent La-201 of extremely high capacity and specific affinity toward phosphate was fabricated and well characterized, where hydrated La(III) oxide (HLO) nanoclusters were immobilized inside the networking pores of the polystyrene anion exchanger D-201. La-201 exhibited enhanced phosphate adsorption in the presence of competing anions (chloride, sulfate, nitrate, bicarbonate, and silicate) at greater levels (up to molar ratio of 20), with working capacity 2-4 times higher than a commercial Fe(III) oxide-based nanocomposite HFO-201 in batch runs. Column adsorption runs by using La-201 could effectively treat ∼6500 bed volumes (BV) of a synthetic feeding solution before breakthrough occurred (from 2.5 mg P/L in influent to <0.5 mg P/L in effluent), approximately 11 times higher magnitude than that of HFO-201. The exhausted La-201 could be regenerated with NaOH-NaCl binary solution at 60 °C for repeated use without any significant capacity loss. The underlying mechanism for the specific sorption of phosphate by La-201 was revealed with the aid of STEM-EDS, XPS, XRD, and SSNMR analysis, and the formation of LaPO4·xH2O is verified to be the dominant pathway for selective phosphate adsorption by the immobilized nano-HLO. The results indicated that La-201 was very promising in highly efficient removal of phosphate from contaminated waters.

Arsenate Adsorption by Hydrous Ferric Oxide Nanoparticles Embedded in Cross-linked Anion Exchanger: Effect of the Host Pore Structure

Three composite adsorbents were fabricated via confined growth of hydrous ferric oxide (HFO) nanoparticles within cross-linked anion exchangers (NS) of different pore size distributions to investigate the effect of host pore structure on the adsorption of As(V). With the decrease in the average pore size of the NS hosts from 38.7 to 9.2 nm, the mean diameter of the confined HFO nanoparticles was lessened from 31.4 to 11.6 nm as observed by transmission electron microscopy (TEM), while the density of active surface sites was increased due to size-dependent effect proved by potentiometric titration. The adsorption capacity of As(V) yielded by Sips model was elevated from 24.2 to 31.6 mg/g via tailoring the pore size of the NS hosts, and the adsorption kinetics was slightly accelerated with the decrease of pore size in background solution containing 500 mg/L of Cl(-). Furthermore, the enhanced adsorption of As(V) was achieved over a wide pH range from 3 to 10, as well as in the presence of competing anions including Cl(-), SO4(2-), HCO3(-), NO3(-) (up to 800 mg/L), and PO4(3-) (up to 10 mg P/L). In addition, the fixed-bed working capacity increased from 2200 to 2950 bed volumes (BV) owing to the size confinement effect, which did not have adverse effect on the desorption of As(V) as the cumulative desorption efficiency reached 94% with 10 BV of binary solution (5% NaOH + 5% NaCl) for all the three adsorbents. Therefore, this study provided a promising strategy to regulate the reactivity of the nanoparticles via the size confinement effect of the host pore structure.

Enhanced removal of EDTA-chelated Cu(II) by polymeric anion-exchanger supported nanoscale zero-valent iron

In this study, a polymeric anion exchanger (D201) was utilized as the support for nanoscale zero-valent iron (NZVI), and the resultant nanocomposite (D201-ZVI) was employed to remove EDTA-chelated Cu(II) from water. The removal of EDTA-chelated Cu(II) was significantly enhanced by D201-ZVI in comparison with NZVI over a wide pH range from 5 to 9. Most of the removed Cu (97.2%) was immobilized inside the D201-ZVI beads, implying the enhanced permeation of CuEDTA2- by the fixated quaternary ammonium groups of the host D201. HPLC analysis revealed that the EDTA-chelated Cu(II) was gradually replaced by Fe(III) originated from Fe0 oxidation. Then, the released Cu(II) was in situ removed via adsorption/precipitation, or further reduced into Cu0, as quantified by XPS spectra. The higher removal of EDTA-chelated Cu(II) by D201-ZVI than NZVI was mainly ascribed to the enhanced permeation of the host D201 as well as to the better dispersion and higher reactivity of the confined ZVI nanoparticles. Through the combination of periodic regeneration and complete regeneration, D201-ZVI could be sustainably employed for EDTA-chelated Cu(II) removal. Also, D201-ZVI exhibited great potential for practical application in the fixed-bed column operation. Therefore, the D201-ZVI nanocomposite was promising in highly efficient removal of EDTA-chelated Cu(II) from water.

Temporospatial evolution and removal mechanisms of As(V) and Se(VI) in ZVI column with H2O2 as corrosion accelerator

Enhanced removal of As(V) and Se(VI) by zero valent iron (ZVI) has been recently revealed by using H2O2 as the corrosion accelerator, however, the detailed performance of such enhanced removal in ZVI column as well as the underlying mechanism is still unclear. In this study, the temporospatial evolution of As(V) and Se(VI) along a self-designed ZVI/H2O2 column in down-flow mode was systematically investigated. The variations of concerned aqueous parameters (pH, ORP, H2O2, Fe2+, As, and Se) were monitored at different positions along the column throughout the experiments. Results showed the corrosion degree of ZVI decreased with the depth of the column, as confirmed by SEM and XRD analyses of the solid samples from different layers. The retention of As and Se also decreased along the column, suggesting the uptake of As(V) and Se(VI) was highly dependent upon the ZVI corrosion evolution. In the initial stage, the influent H2O2 was mostly consumed by ZVI in the top layer. With the continuous corrosion of ZVI, the breakthrough of H2O2 would activate the ZVI at lower positions, resulting in the reactive zone continuously shifting downward along the column. The reduction of As(V) and Se(VI) to aqueous As(III) and Se(IV) was significantly inhibited at the positions in the presence of H2O2, whereas favorably enhanced in the presence of abundant Fe2+. The retention of As(III) in the lower part of the column was observed while that of Se(IV) was negligible, as related to the different effects of pH on the adsorption of As(III) and Se(IV). In addition, the evolution of different oxidation states of As and Se retained in the column were identified by XPS, further demonstrating the comprehensive mechanisms of As(V)/Se(VI) removal involving reduction and adsorption in the ZVI/H2O2 column.

Chromium speciation in tannery effluent after alkaline precipitation: Isolation and characterization.

It is difficult to completely remove Cr(III) from tannery effluent by alkaline precipitation due to the abundance of strong organic ligands. Thereby, the speciation of the residual Cr after alkaline precipitation is of crucial significance to guide the selection and design of further treatment process. For the first time, we revealed the speciation of the residual Cr with the aid of comprehensive analytical techniques. Results showed that the residual Cr(III) mostly located in two size ranges, i.e. the 13-100nm fraction and the <4nm fraction. Combined spectral analyses demonstrated Cr(III) was coordinated by carboxyl groups or hydroxyl groups in both fractions, while the complexation by nitrogen-containing groups was excluded by the total nitrogen and UPLC-MS analysis in the two fractions, respectively. Based on the comprehensive analyses, the structures of Cr(III) complexes in both fractions were proposed. Cr(III) cross-linked the carboxyl groups from polyacrylic acid chains to form the network gel structure in the 13-100nm fraction, while the complex structure of Cr(III) in the <4nm fraction was formed through hydroxyl-carboxyl chelation by masking agents such as tartrate and citrate. Although polyoxyethylene ether was abundantly present, it was responsible for the complexation of Cr(III) in neither fraction.

Flat Graphene-Enhanced Electron Transfer Involved in Redox Reactions

Graphene is easily warped in the out-of-plane direction because of its high in-plane Youngs modulus, and exploring the influence of wrinkled graphene on its properties is essential for the design of graphene-based materials for environmental applications. Herein, we prepared wrinkled graphene (WGN-1 and WGN-2) by thermal treatment and compared their electrochemical properties with those of flat graphene nanosheets (FGN). FGN exhibit activities that are much better than those of wrinkled graphene nanosheets (WGN), not only in the electrochemical oxidation of methylene blue (MB) but also in the electrochemical reduction of nitrobenzene (NB). Transformation ratios of MB and NB in FGN, WGN-1, and WGN-2 were 97.5, 80.1, and 57.9% and 94.6, 92.1, and 81.2%, respectively. Electrochemical impedance spectroscopy and the surface resistance of the graphene samples increased in the following order: FGN < WGN-1 < WGN-2. This suggests that the reaction charges transfer faster across the reaction interfaces and along the surface of FGN than that of WGN, and wrinkles restrict reaction charge transfer and reduce the reaction rates. This study reveals that the morphology of the graphene (flat or wrinkle) greatly affects redox reaction activities and may have important implications for the design of novel graphene-based nanostructures and for our understanding of graphene wrinkle-dependent redox reactions in environmental processes.

Fe(III)-Doped g-C3N4 Mediated Peroxymonosulfate Activation for Selective Degradation of Phenolic Compounds via High-Valent Iron-Oxo Species

Herein, we proposed a new peroxymonosulfate (PMS) activation system employing the Fe(III) doped g-C3N4 (CNF) as catalyst. Quite different from traditional sulfate radical-based advanced oxidation processes (SR-AOPs), the PMS/CNF system was capable of selectively degrading phenolic compounds (e.g., p-chlorophenol, 4-CP) in a wide pH range (3-9) via nonradical pathway. The generated singlet oxygen (1O2) in the PMS/CNF3 (3.46 wt % Fe) system played negligible role in removing 4-CP, and high-valent iron-oxo species fixated in the nitrogen pots of g-C3N4 (≡FeV═O) was proposed as the dominant reactive species by using dimethyl sulfoxide as a probe compound. The mechanism was hypothesized that PMS was first bound to the Fe(III)-N moieties to generate ≡FeV═O, which effectively reacted with 4-CP via electron transfer. GC-MS analysis indicated that 4-chlorocatechol and 1,4-benzoquinone were the major intermediates, which could be further degraded to carboxylates. The kinetic results suggested that the formation of ≡FeV═O was proportional to the dosages of PMS and CNF3 under the experimental conditions. Also, the PMS/CNF3 system exhibited satisfactory removal of 4-CP in the presence of inorganic anions and natural organic matters. We believe that this study will provide a new routine for effective PMS activation by heterogeneous iron-complexed catalysts to efficiently degrade organic contaminants via nonradical pathway.

Environmentally Friendly in Situ Regeneration of Graphene Aerogel as a Model Conductive Adsorbent

Adsorption is a classical process widely used in industry and environmental protection, and the regeneration of exhausted adsorbents, as the reverse process of adsorption, is vital to achieving a sustainable adsorption process. Chemical and thermal regeneration, which feature high costs and environmental side effects, are classical but not environmentally friendly methods. Herein, a new regeneration method based on an electrochemical process using graphene aerogel (GA) as a model conductive adsorbent was proposed. First, 3D GA was prepared to adsorb organic and inorganic pollutants, avoiding the inconvenience of using powdered graphene. Then, the exhausted GA was cleaned by the electrochemical desorption and degradation of adsorbed organic pollutants if undesired and the electrorepulsion of adsorbed metal ions in the absence of any additional chemicals, showing a high processing capability of 1.21 L g-1 GA h-1 and low energy consumption (∼0.2 kWh m-3 solution). The mechanisms involved in the electrochemistry-induced desorption process cover a decline in the GA adsorption performance depended on the electrochemically adjustable surface charge conditions, and the further repulsion and migration of adsorbates is subject to the strong in situ electric field. This work has important implications for the development of environmentally friendly regeneration processes and qualified adsorbents as well as the application of a green and efficient regeneration concept for traditional adsorption processes.

Enhanced removal of Se(VI) from water via pre-corrosion of zero-valent iron using H2O2/HCl: Effect of solution chemistry and mechanism investigation

Although the removal of Se(VI) from water by using zero-valent iron (ZVI) is a promising method, passivation of ZVI severely inhibits its performance. To overcome such issue, we proposed an efficient technique to enhance Se(VI) removal via pre-corrosion of ZVI with H2O2/HCl in a short time (15 min). The resultant pcZVI suspension was weakly acidic (pH 4.56) and contained abundant aqueous Fe2+. 57Fe Mössbauer spectroscopy showed that pcZVI mainly consisted of Fe0 (66.2%), hydrated ferric oxide (26.3%), and Fe3O4 (7.5%). Efficient removal of Se(VI) from sulfate-rich solution was achieved by pcZVI compared with ZVI (in the absence and presence of H2O2) and acid-pretreated ZVI. Moreover, the efficient removal of Se(VI) by pcZVI sustained over a broad pH range (3-9) due to its strong buffering power. The presence of chloride, carbonate, nitrate, and common cations (Na+, K+, Ca2+, and Mg2+) posed negligible influence on the removal of Se(VI) by pcZVI, while the inhibitory effect induced by sulfate, silicate, and phosphate indicated the significance of Se(VI) adsorption as a prerequisite step for its removal. The consumption of aqueous Fe2+ was associated with Se(VI) removal, and X-ray absorption near edge structure revealed that the main pathway for Se(VI) removal by pcZVI was a stepwise reduction of Se(VI) to Se(IV) and then Se0 as the dominant final state (78.2%). Moreover, higher electron selectivity of pcZVI was attributed to the enhanced enrichment of Se oxyanions prior to their reduction.

Enhanced Nitrobenzene reduction by zero valent iron pretreated with H2O2/HCl

In this study a novel iron-based reducing agent of highly effective reduction toward nitrobenzene (NB) was obtained by pretreating zero valent iron (ZVI) with H2O2/HCl. During the H2O2/HCl pretreatment, ZVI undergoes an intensive corrosion process with formation of various reducing corrosion products (e.g., Fe2+, ferrous oxides/hydroxides, Fe3O4), yielding a synergetic system (prtZVI) including liquid, suspensions and solid phase. The pretreatment process remarkably enhances the reductive performance of ZVI, where a rapid reduction of NB (200 mg L-1) in the prtZVI suspension was accomplished in a broad pH range (3-9) and at low dosage. Nitrosobenzene and phenylhydroxylamine are identified as the intermediates for NB reduction with the end-product of aniline. Compared with the virgin ZVI as well as another nanosized ZVI, the prtZVI system exhibits much higher electron efficiency for NB reduction as well as higher utilization ratio of Fe0. A rapid reduction of various nitroaromatics in an actual pharmaceutical wastewater further demonstrated the feasibility of the prtZVI system in real wastewater treatment.