Hongshin Lee

Magnetic mesoporous materials for removal of environmental wastes

We have synthesized two different magnetic mesoporous materials that can be easily separated from aqueous solutions by applying a magnetic field. Synthesized magnetic mesoporous materials, Mag-SBA-15 (magnetic ordered mesoporous silica) and Mag-OMC (magnetic ordered mesoporous carbon), have a high loading capacity of contaminants due to high surface area of the supports and high magnetic activity due to the embedded iron oxide particles. Application of surface-modified Mag-SBA-15 was investigated for the collection of mercury from water. The mercury adsorption using Mag-SBA-15 was rapid during the initial contact time and reached a steady-state condition, with an uptake of approximately 97% after 7h. Application of Mag-OMC for collection of organics from water, using fluorescein as an easily trackable model analyte, was explored. The fluorescein was absorbed into Mag-OMC within minutes and the fluorescent intensity of solution was completely disappeared after an hour. In another application, Mag-SBA-15 was used as a host of tyrosinase, and employed as recyclable catalytic scaffolds for tyrosinase-catalyzed biodegradation of catechol. Crosslinked tyrosinase in Mag-SBA-15, prepared in a two step process of tyrosinase adsorption and crosslinking, was stable enough for catechol degradation with no serious loss of enzyme activity. Considering these results of cleaning up water from toxic inorganic and organic contaminants, magnetic mesoporous materials have a great potential to be employed for the removal of environmental contaminants and potentially for the application in large-scale wastewater treatment plants.

pH-Dependent reactivity of oxidants formed by iron and copper-catalyzed decomposition of hydrogen peroxide

The decomposition of hydrogen peroxide catalyzed by iron and copper leads to the generation of reactive oxidants capable of oxidizing various organic compounds. However, the specific nature of the reactive oxidants is still unclear, with evidence suggesting the production of hydroxyl radical or high-valent metal species. To identify the reactive species in the Fenton system, the oxidation of a series of different compounds (phenol, benzoic acid, methanol, Reactive Black 5 and arsenite) was studied for iron- and copper-catalyzed reactions at varying pH values. At lower pH values, more reactive oxidants appear to be formed in both iron and copper-catalyzed systems. The aromatic compounds, phenol and benzoic acid, were not oxidized under neutral or alkaline pH conditions, whereas methanol, Reactive Black 5, and arsenite were oxidized to a different degree, depending on the catalytic system. The oxidants responsible for the oxidation of compounds at neutral and alkaline pH values are likely to be high-valent metal complexes of iron and copper (i.e., ferryl and cupryl ions).

Magnetite/mesocellular carbon foam as a magnetically recoverable fenton catalyst for removal of phenol and arsenic

A magnetite-loaded mesocellular carbonaceous material, Fe(3)O(4)/MSU-F-C, exhibited superior activity as both a Fenton catalyst and an adsorbent for removal of phenol and arsenic, and strong magnetic property rendering it separable by simply applying magnetic field. In the presence of hydrogen peroxide, the catalytic process by Fe(3)O(4)/MSU-F-C completely oxidized phenol and As(III) under the conditions where commercial iron oxides showed negligible effects. Notably, the decomposition of H(2)O(2) by Fe(3)O(4)/MSU-F-C was not faster than those by commercial iron oxides, indicating that hydroxyl radical produced via the catalytic process by Fe(3)O(4)/MSU-F-C was used more efficiently for the oxidation of target contaminants compared to the other iron oxides. The homogeneous Fenton reaction by the dissolved iron species eluted from Fe(3)O(4)/MSU-F-C was insignificant. At relatively high doses of Fe(3)O(4)/MSU-F-C, total concentration of arsenic decreased to a significant extent due to the adsorption of arsenic on the catalyst surface. The removal of arsenic by adsorption was found to proceed via preoxidation of As(III) into As(V) and the subsequent adsorption of As(V) onto the catalyst.

Oxidant production from corrosion of nano- and microparticulate zero-valent iron in the presence of oxygen: a comparative study.

In aqueous solution, zero-valent iron (ZVI, Fe(0)) is known to activate oxygen (O2) into reactive oxidants such as hydroxyl radical and ferryl ion capable of oxidizing contaminants. However, little is known about the effect of the particle size of ZVI on the yield of reactive oxidants. In this study, the production of reactive oxidants from nanoparticulate and microparticulate ZVIs (denoted as nZVI and mZVI, respectively) was comparatively investigated in the presence of O2 and EDTA. To quantify the oxidant yield, excess amount of methanol was employed, and the formation of its oxidation product, formaldehyde (HCHO), was monitored. The concentration of HCHO in the nZVI/O2 system rapidly reached the saturation value, whereas that in the mZVI/O2 system gradually increased throughout the entire reaction time. The mZVI/O2 system exhibited higher yields of HCHO than the nZVI/O2 system under both acidic and neutral pH conditions. The higher oxidant yields in the mZVI/O2 system are mainly attributed to the less reactivity of the mZVI surface with hydrogen peroxide (H2O2) relative to the surface of nZVI, which minimize the loss of H2O2 by ZVI (i.e., the two-electron reduction of H2O2 into water). In addition, the slow dissolution of Fe(II) from mZVI was found to be partially responsible for the higher oxidant yields at neutral pH.

Microbial inactivation by cupric ion in combination with H2O2: role of reactive oxidants.

The cupric ion mediated inactivation of Escherichia coli was enhanced by the presence of hydrogen peroxide (H2O2), with increasing inactivation efficacy observed in response to increasing concentrations of H2O2. The biocidal activity of the Cu(II)/H2O2 system is believed to result from the oxidative stress caused by reactive oxidants such as the hydroxyl radical ((•)OH), cupryl species (Cu(III)), and the superoxide radical (O2(•-)), which are produced via the catalytic decomposition of H2O2. In E. coli cells treated with Cu(II) and H2O2, the intracellular level of (•)OH and Cu(III) increased significantly, leading to complete disruption of cell membranes. On the basis of experimental observations made using an (•)OH scavenger, copper-chelating agents, and superoxide dismutase, it is concluded that Cu(III) is the predominant species responsible for the death of E. coli cells. It was also found that the production of Cu(III) was promoted by the reactions of copper with intracellular O2(•-). MS2 coliphage was found to be even more susceptible than E. coli to the oxidative stress induced by the Cu(II)/H2O2 system.

Oxidizing capacity of periodate activated with iron-based bimetallic nanoparticles.

Nanosized zerovalent iron (nFe0) loaded with a secondary metal such as Ni or Cu on its surface was demonstrated to effectively activate periodate (IO4-) and degrade selected organic compounds at neutral pH. The degradation was accompanied by a stoichiometric conversion of IO4- to iodate (IO3-). nFe0 without bimetallic loading led to similar IO4- reduction but no organic degradation, suggesting the production of reactive iodine intermediate only when IO4- is activated by bimetallic nFe0 (e.g., nFe0-Ni and nFe0-Cu). The organic degradation kinetics in the nFe0-Ni(or Cu)/IO4- system was substrate dependent: 4-chlorophenol, phenol, and bisphenol A were effectively degraded, whereas little or no degradation was observed with benzoic acid, carbamazepine, and 2,4,6-trichlorophenol. The substrate specificity, further confirmed by little kinetic inhibition with background organic matter, implies the selective nature of oxidant in the nFe0-Ni(or Cu)/IO4- system. The comparison with the photoactivated IO4- system, in which iodyl radical (IO3•) is a predominant oxidant in the presence of methanol, suggests IO3• also as primary oxidant in the nFe0-Ni(or Cu)/IO4- system.

Polyphosphate-enhanced production of reactive oxidants by nanoparticulate zero-valent iron and ferrous ion in the presence of oxygen: Yield and nature of oxidants

The production of reactive oxidants from nanoparticulate zero-valent iron (nZVI) and ferrous ion (Fe(II)) in the presence of oxygen was greatly enhanced by the addition of tetrapolyphosphate (TPP) as an iron-chelating agent. Compared to other ligands, TPP exhibited superior activity in improving the oxidant yields. The nZVI/TPP/O2 and the Fe(II)/TPP/O2 systems showed similar oxidant yields with respect to the iron consumed, indicating that nZVI only serves as a source of Fe(II). The degradation efficacies of selected organic compounds were also similar in the two systems. It appeared that both hydroxyl radical (OH) and ferryl ion (Fe(IV)) are produced, and OH dominates at acidic pH. However, at pH > 6, little occurrence of hydroxylated oxidation products suggests that Fe(IV) is a dominant oxidant. The degradation rates of selected organic compounds by the Fe(II)/TPP/O2 system had two optimum points at pH 6 and 9, and these pH-dependent trends are likely attributed to the speciation of Fe(IV) with different reactivities.

Activation of Oxygen and Hydrogen Peroxide by Copper(II) Coupled with Hydroxylamine for Oxidation of Organic Contaminants

This study reports that the combination of Cu(II) with hydroxylamine (HA) (referred to herein as Cu(II)/HA system) in situ generates H2O2 by reducing dissolved oxygen, subsequently producing reactive oxidants through the reaction of Cu(I) with H2O2. The external supply of H2O2 to the Cu(II)/HA system (i.e., the Cu(II)/H2O2/HA system) was found to further enhance the production of reactive oxidants. Both the Cu(II)/HA and Cu(II)/H2O2/HA systems effectively oxidized benzoate (BA) at pH between 4 and 8, yielding a hydroxylated product, p-hydroxybenzoate (pHBA). The addition of a radical scavenger, tert-butyl alcohol, inhibited the BA oxidation in both systems. However, electron paramagnetic resonance (EPR) spectroscopy analysis indicated that (•)OH was not produced under either acidic or neutral pH conditions, suggesting that the alternative oxidant, cupryl ion (Cu(III)), is likely a dominant oxidant.

Enhanced Inactivation of Escherichia coli and MS2 Coliphage by Cupric Ion in the Presence of Hydroxylamine: Dual Microbicidal Effects

The inactivation of Escherichia coli and MS2 coliphage by Cu(II) is found to be significantly enhanced in the presence of hydroxylamine (HA). The addition of a small amount of HA (i.e., 5-20 μM) increased the inactivation efficacies of E. coli and MS2 coliphage by 5- to 100-fold, depending on the conditions. Dual effects were anticipated to enhance the biocidal activity of Cu(II) by the addition of HA, viz. (i) the accelerated reduction of Cu(II) into Cu(I) (a stronger biocide) and (ii) the production of reactive oxidants from the reaction of Cu(I) with dissolved oxygen (evidenced by the oxidative transformation of methanol into formaldehyde). Deaeration enhanced the inactivation of E. coli but slightly decreased the inactivation efficacy of MS2 coliphage. The addition of 10 μM hydrogen peroxide (H2O2) greatly enhanced the MS2 inactivation, whereas the same concentration of H2O2 did not significantly affect the inactivation efficacy of E. coli Observations collectively indicate that different biocidal actions lead to the inactivation of E. coli and MS2 coliphage. The toxicity of Cu(I) is dominantly responsible for the E. coli inactivation. However, for the MS2 coliphage inactivation, the oxidative damage induced by reactive oxidants is as important as the effect of Cu(I).

Response to Comment on “Activation of Persulfate by Graphitized Nanodiamonds for Removal of Organic Compounds”

■ RADICAL SPECIES Regarding the controversial issues on the mechanism of persulfate activation by carbon materials (i.e., radical versus nonradical pathways), either of the two pathways cannot be completely excluded. What matters is which pathway is more dominant. After a comprehensive review of our experimental data, we have concluded that the nonradical pathway is the dominant mechanism of persulfate activation by graphitized nanodiamonds (G-NDs). About the effects of radical scavengers, Duan et al. criticized that the dose of radical scavengers used in our study (200 mM) was too low. They particularly pointed out that the concentration of radical scavenger was only 200 times that of persulfate; but what matters here is the concentration relative to, not persulfate, but radicals which is at many orders of magnitude lower concentration. We believe that the scavenger dose is sufficient to quench most of radicals, also considering its diffusion-limited reaction kinetics with radicals. Whether the observed inhibition of phenol oxidation by radical scavengers is significant or not may need further discussion, since that there are indeed some uncertainties about the effects of high-dose radical scavengers on the nonradical oxidation of phenol. Related to this discussion, we note that Duan et al. made inconsistent interpretations on the inhibitory effects of radical scavengers in their own studies. For example, in one study on N-doped CNTs, they emphasized the nonradical mechanism and stated that “NoCNT-350 and NoCNT-700 still maintained excellent phenol degradation ef f iciency at a high concentration of radical quenching agent with PMS”, whereas they suggested a radical mechanism in another study on N-modified nanodiamonds, stating that “the remarkable decrease in the rate constants in this study suggests that the reactive radicals played dominant roles in phenol degradation”. However, comparing the experimental results of those two studies, the inhibitory effects of radical scavengers were in fact greater for N-doped CNTs than N-modified NDs. We have no explanation for the discrepancy in electron paramagnetic resonance (EPR) data between ours and Duan et al.’s. It may be attributed to the differences in experimental conditions (including possible differences in carbon materials). It should be noted that the detection of radical signals does not guarantee that the radical pathway prevails against the nonradical pathway. We note that the EPR data in Duan et al.’ study did not show any significant difference in the signal intensity between annealed and pristine nanodiamonds even though the rates of phenol oxidation on the two materials were immensely different, which raises a question about the role of radical species on phenol oxidation. Also note that the EPR analysis using spin-trapping agents is often imperfect to identify radical species because the spin adduct can be formed through different pathways. As described in our study, the negligible oxidation of benzoic acid (its minor removal was found to be due to the adsorption) indicates that the radical pathway is not important. Duan et al. also observed that the removal efficiency of benzoic acid is very low in their system; this minor removal might be also due to the adsorption onto the carbon material. Additional experimental data showed that the oxidation of benzoic acid by the UV−C/persulfate system (a well-known SO4 source) proceeded at a similar rate to that of phenol (Figure 1a). If sulfate radical were a predominant oxidant as Duan et al. claimed, one should observe similar oxidation of benzoic acid in G-ND/persulfate system.