Huachun Lan

Heterogeneous photo-Fenton degradation of acid red B over Fe2O3 supported on activated carbon fiber.

Fe2O3 supported on activated carbon fiber (Fe2O3/ACF) was prepared via an impregnation method and characterized by X-ray diffraction, scanning electron microscopy and BET analysis. The results indicated that Fe2O3 with small particle size was highly dispersed on the surface of the ACF and the introduction of Fe2O3 did not change the ACF pore structure. Fe2O3/ACF exhibited a higher Fenton efficiency for the degradation of acid red B (ARB), especially under simulated solar irradiation. Complete decoloration of the ARB solution and 43% removal of TOC could be achieved within 200 min under optimal conditions. It was verified that more ˙OH radicals were generated in the photo-assisted Fenton process and involved as active species in ARB degradation. FTIR analysis indicated that the degradation of ARB was initiated through the cleavage of -N=N-, followed by hydroxylation and opening of phenyl rings to form aliphatic acids, and further oxidation of aliphatic acids would produce CO2 and H2O. Moreover, Fe2O3/ACF maintained its activity after being reused 4 times and the release of iron from the catalyst was found to be insignificant during the Fenton and photo-Fenton processes, indicating that Fe2O3/ACF had good long-term stability.

Photoelectrochemical treatment of landfill leachate in a continuous flow reactor

Leachate from a municipal landfill site, which has been treated by biological process, was treated by photoelectrochemical oxidation in a pilot scale flow reactor, using DSA anode and UV light irradiation. At a current density of 67.1mA/cm(2) and 2.5h reaction time, the removal rates achieved were for 74.1% COD, 41.6% for TOC, and 94.5% for ammonium in the electrolysis process with UV light irradiation. In comparison, the removal rates of COD, TOC, and ammonium were decreased in the individual electrolysis process, respectively. The increase induced by the UV light irradiation was analyzed. The removal rates increased with the increase of current densities in the photoelectrochemical process. Combined with UV-vis spectra and gas chromatography-mass spectroscopy analysis, it is believed that the organic contaminants were efficiently mineralized into small molecular acids. At the meantime, the concentrations of metal ions in the landfill leachate were largely reduced.

Preparation of amino-Fe(III) functionalized mesoporous silica for synergistic adsorption of tetracycline and copper

Finding effective methods for simultaneous removal of antibiotics and heavy metals has attracted increasing concern since both of them are frequently detected in aquatic environments. In this study, a novel mesoporous silica adsorbent (Fe-N,N-SBA15) contained dual-functional groups was synthesized by first grafting di-amino groups on SBA15, and then coordinating Fe(III) onto the adsorbent. The adsorbent was then used in the synchronous elimination of tetracycline (TC) and Cu(II) from water, which was deeply studied by solution pH, kinetics, equilibriums in sole and binary systems. It was found that the adsorbent had high affinity for both TC and Cu(II) and synergistic effects on the adsorption were found. The solution pH remarkably affected the adsorption due to pH-dependent speciation of TC, Cu(II), TC-Cu(II) complex and the surface properties of the adsorbent. Increasing adsorption amount of TC and Cu(II) on the adsorbent could be attributed to the formation of complex TC-Cu(II) bridging or the stronger affinity of the adsorbent for the TC-Cu(II) complex than that for TC or Cu(II) separately. FT-IR and XPS studies revealed that Fe(III) and amino groups on the adsorbent were complexed with the amide of TC and Cu(II), respectively. The recyclabilities of the adsorbent were also evaluated and the Fe-N,N-SBA15 exhibited good reusability for TC and Cu(II) removal. This study shows guidelines and offers an innovative, effective method for the synergistic removal of antibiotics and heavy metals from aquatic environments.

Dechlorination of Trichloroacetic Acid Using a Noble Metal-Free Graphene–Cu Foam Electrode via Direct Cathodic Reduction and Atomic H*

A three-dimensional graphene-copper (3D GR-Cu) foam electrode prepared by chemical vapor deposition method exhibited superior electrocatalytic activity toward the dechlorination of trichloroacetic acid (TCAA) as compared to the Cu foam electrode. The cyclic voltammetry and electrochemical impedance spectra analysis confirmed that GR accelerated the electron transfer from the cathode surface to TCAA. With the applied cathode potential of -1.2 V (vs SCE), 95.3% of TCAA (500 μg/L) was removed within 20 min at pH 6.8. TCAA dechlorination at the Cu foam electrode was enhanced at acidic pH, while a slight pH effect was observed at the GR-Cu foam electrode with a significant inhibition for Cu leaching. The electrocatalytic dechlorination of TCAA was accomplished via a combined stepwise and concerted pathway on both electrodes, whereas the concerted pathway was efficiently promoted on the GR-Cu foam electrode. The direct reduction by electrons was responsible for TCAA dechlorination at Cu foam electrode, while at GR-Cu foam electrode, the surface-adsorbed atomic H* also contributed to TCAA dechlorination owing to the chemical storage of hydrogen in the GR structure. Finally, the potential applicability of GR-Cu foam was revealed by its stability in the electrocatalytic dechlorination over 25 cycles.

An activated carbon fiber cathode for the degradation of glyphosate in aqueous solutions by the Electro-Fenton mode: Optimal operational conditions and the deposition of iron on cathode on electrode reusability

An activated carbon fiber (ACF) cathode was fabricated and used to treat glyphosate containing wastewater by the Electro-Fenton (EF) process. The results showed that glyphosate was rapidly and efficiently degraded and the BOD5/COD ratio was increased to >0.3 implying the feasibility of subsequent treatment of the treated wastewater by biological methods. The results of ion chromatography and HPLC measurements indicated that glyphosate was completely decomposed. Effective OH generation and rapid recycling/recovery of the Fe2+ ions at the cathode were responsible primarily for the high performance of the ACF-EF process. Factors such as inlet oxygen gas flow rate, Fe2+ dosage, initial glyphosate concentration, applied current intensity, and solution pH that may affect the efficiency of the ACF-EF process were further studied and the optimum operation condition was established. Results of SEM/EDX, BET and XPS analysis showed the deposition of highly dispersed fine Fe2O3 particles on the ACF surface during the EF reaction. The possibility of using the Fe2O3-ACF as iron source in the EF process was assessed. Results showed that the Fe2O3-ACF electrode was effective in degrading glyphosate in the EF process. The deposition of Fe2O3 particles on the ACF electrode had no adverse effect on the reusability of the ACF cathode.

Adsorption of antimony(V) onto Mn(II)-enriched surfaces of manganese-oxide and FeMn binary oxide.

Manganese(IV) oxide [Mn(IV)] potentially oxidizes antimony(III) [Sb(III)] to antimony(V) [Sb(V)] and improves Sb removal by FeMn binary oxide (FMBO) through an oxidation-adsorption mechanism. This study focused on the effect of Mn(IV) reductive dissolution by potassium sulfite (K2SO3) on Sb(V) adsorption onto manganese oxide (Mn-oxide) and FMBO. The maximum Sb(V) adsorption (Qmax,Sb(V)) increased from 1.0 to 1.1 mmol g(-1) for FMBO and from 0.4 to 0.6 mmol g(-1) for Mn-oxide after pretreatment with 10 mmol L(-1) K2SO3. The addition of 2.5 mmol L(-1) Mn(2+) also significantly improved Sb(V) adsorption, and the observed Qmax,Sb(V) increased to 1.4 and 1.0 mmol g(-1) for FMBO and Mn-oxide, respectively, with pre-adsorbed Mn(2+). Neither K2SO3 nor Mn(2+) addition had any effect on Sb(V) adsorption onto iron oxide (Fe-oxide). Mn(2+) introduced by either Mn(IV) dissolution or addition tended to form outer-sphere surface complexes with hydroxyl groups on Mn-oxide surfaces (MnOOH). Mn(2+) at 2.5 mmol L(-1) shifted the isoelectric point (pHiep) from 7.5 to 10.2 for FMBO and from 4.8 to 9.2 for Mn-oxide and hence benefited Sb(V) adsorption. The adsorption of Sb(V) onto Mn(2+)-enriched surfaces contributed to the release of Mn(2+), and the X-ray photoelectron spectra also indicated increased binding energy of Mn 2p3/2 after the adsorption of Sb(V) onto K2SO3-pretreated FMBO and Mn-oxide. Sb(V) adsorption involved the formation of inner-sphere complexes and contributed to the release of Mn(2+). In the removal of Sb(III) by Mn-based oxides, the oxidation of Sb(III) to Sb(V) by Mn(IV) oxides had an effect; however, Mn(IV) dissolution and Mn(2+)-enrichment also played an important role.

Graphene-modified Pd/C cathode and Pd/GAC particles for enhanced electrocatalytic removal of bromate in a continuous three-dimensional electrochemical reactor

Bromate (BrO3(-)) is a carcinogenic and genotoxic contaminant commonly generated during ozonation of bromide-containing water. In this work, the reductive removal of BrO3(-) in a continuous three-dimensional electrochemical reactor with palladium-reduced graphene oxide modified carbon paper (Pd-rGO/C) cathode and Pd-rGO modified granular activated carbon (Pd-rGO/GAC) particles was investigated. The results indicated that the rGO sheets significantly promoted the electrochemical reduction of BrO3(-). With the enhanced electron transfer by rGO sheets, the electroreduction of H2O to atomic H* on the polarized Pd particles could be significantly accelerated, leading to a faster reaction rate of BrO3(-) with atomic H*. The synergistic effect of the Pd-rGO/C cathode and Pd-rGO/GAC particles were also exhibited. The atomic H* involved in various electroreduction processes was detected by electron spin resonance spectroscopy and its role for BrO3(-) reduction was determined. The performance of the reactor was evaluated in terms of the removal of BrO3(-) and the yield of Br(-) as a function of the GO concentration, Pd loading amount, current density, hydraulic residence time (HRT), and initial BrO3(-) concentration. Under the current density of 0.9 mA/cm(2), BrO3(-) with the initial concentration of 20 μg/L was reduced to be less than 6.6 μg/L at the HRT of 20 min. The BrO3(-) reduction was inhibited in the presence of dissolved organic matter. Although the precipitates generated from Ca(2+) and Mg(2+) in the tap water would cover the Pd catalysts, a long-lasting electrocatalytic activity could be maintained for the 30 d treatment. SEM and XPS analysis demonstrated that the precipitates were predominantly deposited onto the Pd-rGO/C cathode rather than the Pd-rGO/GAC particles.

Polycyclic aromatic hydrocarbons in effluents from wastewater treatment plants and receiving streams in Tianjin, China.

Surface water, suspended particulate matter, pore water, and sediment samples were collected and analyzed for polycyclic aromatic hydrocarbons (PAHs) in Yongding New River, South Drainage Canal and North Drainage Canal, which receive most of wastewater from industrial city of Tianjin. PAH concentrations in effluent samples of wastewater treatment plants (WTP) discharging into the South Drainage Canal and North Drainage Canal were quantified for the first time. The results showed that the discharge of the WTPs recently only contributed to the PAH contamination in the canals near the outlets of the WTPs. PAH levels in sediments of the streams were greatly higher than those in soils by riverbank probably due to receiving large amounts of untreated wastewater. Unusually high benz[a] anthracene concentration strongly influenced the seasonal and spatial variation of total PAH concentrations in South Drainage Canal. Paired samples t test of ∑Nap, Fl, Phe, Fluo and ∑Nap, Phe, Fluo, Chry concentrations, which were dominant components in the air samples from non-heating and heating season, respectively, in the suspended particulate matters from the streams showed that PAH source from air deposition was more important for Yongding New River than that for South Drainage Canal and North Drainage Canal. Source apportionment based on PAH profiles indicated that coal combustion was the major PAH contamination source, and coke oven sources and wood combustion also contributed to the PAH contamination of the streams. This was further indicated by organic petrography analysis.

Iron-incorporated mesoporous silica for enhanced adsorption of tetracycline in aqueous solution

Fe-incorporated SBA15 (Fe-SBA15) with different contents of Fe(III) was synthesized in order to enhance the adsorption of antibiotic tetracycline (TC) from aqueous solution. The influence of the Fe(III) content on the structural, textural and morphological properties of the adsorbents and the adsorption process of TC were investigated. The results showed that the adsorbents exhibited mesoporous structural order after co-condensation with different ratios of Fe/Si. As the Fe/Si ratio increased from 0.02 to 0.1, the Fe(III) incorporated into the mesoporous silica framework offered abundant active sites for the adsorption of TC. The adsorption behavior was systematically studied and the results showed that Fe-SBA15 had higher adsorption capacity for TC than that of SBA15. The optimized solution pH for the adsorption was around 5.0 to 7.0, and the adsorption was endothermic and spontaneous. The adsorption mechanism mainly involved inner-sphere surface complexes formed between functional groups of TC and the Fe(III) on the adsorbent. The synthesized materials have excellent potential as adsorbents for environmental remediation.

Microfluidic Flow through Polyaniline Supported by Lamellar-Structured Graphene for Mass-Transfer-Enhanced Electrocatalytic Reduction of Hexavalent Chromium

Owing to its high efficiency and environmental compatibility, electroreduction holds great promise for the detoxification of aqueous Cr(VI). However, the typical electroreduction system often shows poor mass transfer, which results in slow reduction kinetics and hence higher energy consumption. Here, we demonstrate a flow-through electrode of polyaniline supported on lamellar-structured graphene (LGS-PANI) for electrocatalytic reduction of Cr(VI). The reaction kinetics of the LGS-PANI flow-through electrodes are 6.4 times (at acidic condition) and 17.3 times (at neutral condition) faster than traditional immersed parallel-plate electrodes. Computational fluid dynamics simulation suggests that the flow-through mode greatly enhances the mass transfer and that the nanoscale convection induced by the PANI nanodots increases the nanoscale mass transport in the interfacial region of the electrode/solution. In situ Raman spectroscopy shows that the PANI-Cr(VI) redox reactions are dominated by the leucoemeraldine/emeraldine transition at 1.5 V cell voltage, which also remarkably contributes to the fast reaction kinetics. Using single-pass flow-through mode, the LGS-PANI electrode reaches an average reduction efficiency of 99.8% with residual Cr(VI) concentration of 22.3 ppb (initial [Cr(VI)] = 10 ppm, flux = 20 L h(-1) m(-2)). A long-term stability test shows that the LGS-PANI maintains stable performance over 40 days of operation and achieves >98% reduction efficiency, with average current efficiency of as high as 99.1% (initial [Cr(VI)] = 10 ppm, flux = 50 L h(-1) m(-2)).