科研成果 by Year: 2019

2019
Ji H, Zhu Y, Duan J, Liu W, Zhao D. Reductive immobilization and long-term remobilization of radioactive pertechnetate using bio-macromolecules stabilized zero valent iron nanoparticles. Chinese Chemical Letters [Internet]. 2019;30:2163 - 2168. 访问链接Abstract
Reductive immobilization of radioactive pertechnetate (99TcO4−) in simulated groundwater was studied by prepared carboxymethyl cellulose (CMC) and starch stabilized zero valent iron nanoparticles (nZVI), and long-term remobilization of reduced Tc was also evaluated under anoxic and oxic conditions. The stabilized nZVI can effectively reduce soluble 99Tc(VII) to insoluble 99Tc(IV), and they can be easily delivered into a contaminated groundwater zone and facilitate in situ remediation. In this study, CMC-stabilized nZVI showed higher reactivity than that using starch as the stabilizer. Batch experiments indicated that more than 99% of 99Tc(VII) (C0=12mg/mL) was reduced and removed from groundwater by CMC-stabilized nZVI with a CMC content of 0.2% (w/w) at a broad pH of 5–8. X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS) analyses further confirmed that 99Tc(VII)O4− transformed into 99Tc(IV)O2 (s). The presence of bicarbonate exhibited insignificant effect on Tc immobilization, while humic acid (HA) inhibited reaction mainly due to retardation on electron transfer and formation of Tc(IV)-HA complexes. More interesting, the immobilized Tc(IV) remained insoluble even after 120 d under anoxic condition, while only ∼21% was remobilized when exposed to air. Therefore, bio-macromolecules stabilized nZVI nanoparticles could be a viable alternative for in situ remediation of radioactive contamination in groundwater.
Liu W, Zhang W, Liu M, Du P, Dang C, Liang J, Li Y. Fabrication of niobium doped titanate nanoflakes with enhanced visible-light-driven photocatalytic activity for efficient ibuprofen degradation. Chinese Chemical Letters [Internet]. 2019;30:2177 - 2180. 访问链接Abstract
In this study, a novel class of niobium (Nb) doped titanate nanoflakes (TNFs) are fabricated through a one-step hydrothermal method. Nb doping affects the curving of titanate nanosheet, leading to the formation of nanoflake structure. In addition, Nb5+ filled in the interlayers of [TiO6] alters the light adsorption property of pristine titanate. The band gap of Nb-TNFs is narrowed to 2.85 eV, while neat titanate nanotubes (TNTs) is 3.4 eV. The enhanced visible light adsorption significantly enhances the visible-light-driven activity of Nb-TNFs for ibuprofen (IBP) degradation. The pseudo-first order kinetics constant for Nb-TNFs is calculated to be 1.04 h−1, while no obvious removal is observed for TNTs. Photo-generated holes (h+) and hydroxyl radicals (OH) are responsible for IBP degradation. The photocatalytic activity of Nb-TNFs depends on pH condition, and the optimal pH value is found to be 5. In addition, Nb-TNFs exhibited superior photo-stability during the reuse cycles. The results demonstrated Nb-TNFs are very promising in photocatalytic water purification.
Ma M, Chen L, Zhao J, Liu W, Ji H. Efficient activation of peroxymonosulfate by hollow cobalt hydroxide for degradation of ibuprofen and theoretical study. Chinese Chemical Letters [Internet]. 2019;30:2191 - 2195. 访问链接Abstract
Hollow microsphere structure cobalt hydroxide (h-Co(OH)2) was synthesized via an optimized solvothermal-hydrothermal process and applied to activate peroxymonosulfate (PMS) for degradation of a typical pharmaceutically active compound, ibuprofen (IBP). The material characterizations confirmed the presence of the microscale hollow spheres with thin nanosheets shell in h-Co(OH)2, and the crystalline phase was assigned to α-Co(OH)2. h-Co(OH)2 could efficiently activate PMS for radicals production, and 98.6% of IBP was degraded at 10 min. The activation of PMS by h-Co(OH)2 was a pH-independent process, and pH 7 was the optimum condition for the activation-degradation system. Scavenger quenching test indicated that the sulfate radical (SO4• −) was the primary reactive oxygen species for IBP degradation, which contributed to 75.7%. Fukui index (f −) based on density functional theory (DFT) calculation predicted the active sites of IBP molecule for SO4• − attack, and then IBP degradation pathway was proposed by means of intermediates identification and theoretical calculation. The developed hollow Co(OH)2 used to efficiently activate PMS is promising and innovative alternative for organic contaminants removal from water and wastewater.
Kim J, Zhang T, Liu W, Du P, Dobson JT, Huang C-H. Advanced Oxidation Process with Peracetic Acid and Fe(II) for Contaminant Degradation. Environmental Science & Technology [Internet]. 2019;53:13312-13322. 访问链接Abstract
Fe(II) is an excellent promoter for advanced oxidation processes (AOPs) because of its environmental ubiquity and low toxicity. This study is among the first to characterize the reaction of peracetic acid (PAA) with Fe(II) ion and apply the Fe(II)/PAA AOP for degradation of micropollutants. PAA reacts with Fe(II) (k = 1.10 × 105–1.56 × 104 M–1 s–1 at pH 3.0–8.1) much more rapidly than H2O2 and outperforms the coexistent H2O2 for reaction with Fe(II). While PAA alone showed minimal reactivity with methylene blue, naproxen, and bisphenol-A, significant abatement (48–98%) of compounds was observed by Fe(II)/PAA at initial pH of 3.0–8.2. The micropollutant degradation by Fe(II)/PAA exhibited two kinetic phases (very rapid then slow) related to PAA and H2O2, respectively. Based on experimental evidence, formation of carbon-centered radicals (CH3C(O)O•, CH3C(O)•, and •CH3), •OH, and Fe(IV) reactive intermediate species from the PAA and Fe(II) reactions in the presence of H2O2 is hypothesized. The carbon-centered radicals and/or Fe(IV) likely played an important role in micropollutant degradation in the initial kinetic phase, while •OH was important in the second reaction phase. The transformation products of micropollutants showed lower model-predicted toxicity than their parent compounds. This study significantly advances the understanding of PAA and Fe(II) reaction and demonstrates Fe(II)/PAA to be a feasible advanced oxidation technology.
Zhou N, Dang C, Zhao Z, He S, Zheng M, Liu W, Wang X. Role of sludge retention time in mitigation of nitrous oxide emission from a pilot-scale oxidation ditch. Bioresource Technology [Internet]. 2019;292:121961. 访问链接Abstract
Nitrous oxide (N2O) emission from wastewater treatment plants (WWTPs) has become a focus of attention due to its significant greenhouse effect. In this study, the role of sludge retention time (SRT) in mitigation of N2O emission from a pilot-scale oxidation ditch was systematically investigated. The activated sludge system that operated at SRT of 25 days demonstrated significantly lower N2O emission factor, higher resistance to ammonia overload and aeration failure shock than those obtained at SRT of 15 days no matter which hydraulic retention time (HRT) was adopted. Batch experiments revealed that nitrifier denitrification (ND) was the primary mechanism of N2O generation. However, more microbes affiliated with Nitrospira genera were harbored in the system at SRT 25 d, which could effectively avoid nitrite accumulation, a key factor promoting N2O generation by ND. PICRUSt results further suggested the system at SRT 25 d possessed higher genetic potential for N2O reduction reflected by the more abundant nitrous-oxide reductase.
Xu X, Liu Y, Wang T, Ji H, Chen L, Li S, Liu W. Co-adsorption of ciprofloxacin and Cu(II) onto titanate nanotubes: Speciation variation and metal-organic complexation. Journal of Molecular Liquids [Internet]. 2019;292:111375. 访问链接Abstract
Titanate nanotubes (TNTs) have been reported to show good adsorption performance for heavy metals, but researches on organic contaminants adsorption by TNTs are limited. In this study, co-adsorption of a heavy metal (Cu) and an emerging organic contaminant (ciprofloxacin, CIP) by TNTs was investigated in binary systems. TNTs could simultaneously remove the two contaminants, with a high adsorption capacity of 234.5 μmol/g for Cu(II) and 237.0 μmol/g for CIP at pH 4 in the binary system. pH greatly affected adsorption due to speciation variation of the contaminants and surface charge change of TNTs. Cu(II)-CIP complexes dominated adsorption capacity and mechanism. Adsorption of CIP was promoted by high concentration of Cu(II) at pH 3–8 due to formation of abundant Cu(CIP±)2+, while inhibited by low concentration of Cu(II) because of competitive adsorption. The adsorption affinity of CIP species to TNTs was ranked as: Cu(CIP±)2+ > CIP+ > CIP± > Cu(CIP±)2+ > Cu(CIP−·CIP±)+ > CIP−. In comparison, the co-existence of CIP slightly affected Cu(II) adsorption considering the strong affinity of Cu2+ to TNTs. X-ray photoelectron spectrometer (XPS) and Fourier transform infrared spectroscopy (FTIR) results further confirmed the formation of Cu(II)-CIP complexes through –NH2Cu/–COOCu linkages. This work not only proposed a feasible technology for co-removal of heavy metals and organics from water, but also presented insight into interaction mechanisms of different contaminants with nanomaterials during adsorption.
Cai Z, Hao X, Sun X, Du P, Liu W, Fu J. Highly active WO3@anatase-SiO2 aerogel for solar-light-driven phenanthrene degradation: Mechanism insight and toxicity assessment. Water Research [Internet]. 2019;162:369 - 382. 访问链接Abstract
The global energy crisis and water pollution drive the researchers to develop highly effective and less energy intensive water purification technologies. In this study, a highly active WO3@TiO2–SiO2 nanocomposite was synthesized and used for photocatalytic degradation of persistent organic pollutants under simulated solar light. The optimum WO3@TiO2–SiO2 prepared with 2 wt% WO3 loading and calcination at 800 °C exhibited higher photocatalytic activity, as the rate constant (k1) for phenanthrene degradation was ∼7.1 times of that for the commercial TiO2 (P25). The extremely large specific surface area (>400 m2/g) of WO3@TiO2–SiO2 afforded it with enlarged pollutants adsorption performance and abundant active surface sites. The heterojunction of anatase with SiO2 as well as loading of WO3 decreased the band gap energy (Eg) of TiO2, which extended the utilization spectrum of TiO2 to visible region. Formation of Ti–O–Si band indicated the excess charges can cause Brønsted acidity due to the absorption of protons to compensate the charges. Moreover, the migration of photo-excited electrons from the conduction band of anatase to WO3 and holes in the opposite direction restrained the electron-hole recombination. The photocatalytic degradation mechanism and pathway for phenanthrene degradation were proposed based on experimental analysis and density functional theory (DFT) calculation, and the toxicities of the degradation intermediates were evaluated by quantitative structure–activity relationship (QSAR) analysis. WO3@TiO2–SiO2 also showed good separation (settling) performance and high stability. Our work is expected to offer new insight into the photocatalytic mechanism for WO3, TiO2 and SiO2 based heterojunctions, and rational design and synthesis of highly efficient photocatalysts for environmental application.
Zhou N, Zhao Z, Wang H, Chen X, Wang M, He S, Liu W, Zheng M. The effects of graphene oxide on nitrification and N2O emission: Dose and exposure time dependent. Environmental Pollution [Internet]. 2019;252:960 - 966. 访问链接Abstract
With the extensive application of graphene oxide (GO), its leakage and release into wastewater treatment plants become inevitable. However, the toxicity of graphene oxide (GO) on nitrification process and the underlying mechanisms still remain unclear. In this study, the toxic effects of GO at concentration of 10 and 100 mg/L in 4 h and 10 days were evaluated with sealed reactors operated in sequencing batch mode. In the initial 4 h, both GO concentrations showed no negative effect on nitrogen conversion. However, the exposure to 100 mg/L GO significantly weakened the NH+ 4-N and NO- 2-N conversion capabilities and intensified the nitrous oxide (N2O) generation after 10 days. Extracellular polymeric substance (EPS) analysis suggested that 100 mg/L GO decreased the protein content of the nitrifying activated sludge. Moreover, reactive oxygen species (ROS) level was promoted by 100 mg/L GO owing to the impaired endogenous antioxidant enzymes including superoxide dismutase (SOD) and catalase (CAT), which caused oxidative stress to bacteria. Finally, quantitative PCR results confirmed that nitrite-oxidizing bacteria (NOB) and complete ammonia oxidizing bacteria (CAOB) were more sensitive to GO, which was the primary cause for the significant promotion of N2O generation in the high GO concentration. This study offered new insights in the toxicity of GO on nitrification and N2O generation in the terms of dose and exposure time.
Chen Q, Chen L, Qi J, Tong Y, Lv Y, Xu C, Ni J, Liu W. Photocatalytic degradation of amoxicillin by carbon quantum dots modified K2Ti6O13 nanotubes: Effect of light wavelength. Chinese Chemical Letters [Internet]. 2019;30:1214 - 1218. 访问链接Abstract
A novel carbon quantum dots modified potassium titanate nanotubes (CQDs/K2Ti6O13) composite photocatalyst was synthesized by hydrothermal treatment combined with calcination. X-ray diffraction (XRD) pattern and transmission electron microscopy (TEM) indicated formation of potassium titanate nanotubes and successful deposition of CQDs onto K2Ti6O13. The photocatalytic performance of CQDs/K2Ti6O13 composite was evaluated by degradation of amoxicillin (AMX) under the irradiation of visible light and lights with the wavelengths of 365, 385, 420, 450, 485, 520, 595 and 630 nm. The results showed that the photocatalytic activity of CQDs/K2Ti6O13 hybrid material was greatly enhanced compared with the neat K2Ti6O13 calcined at 300 °C. The narrowed band gap energy (Eg) and transfer of photo-excited electron by CQDs inhibited the immediate combination of electron-hole pairs, thus promoting photocatalytic activity. Moreover, CQDs/K2Ti6O13 exhibited a broad spectrum of photocatalytic ability and it was interesting that the photocatalytic activity decreased with the increase of the irradiation wavelength. Reactive oxygen species (ROS) quenching tests suggested the hole (h+) and hydroxyl radical (OH) played the primary roles in photocatalytic degradation of AMX. Moreover, CQDs/K2Ti6O13 showed good reusability for AMX photocatalytic degradation after five successive runs. This study proposed an available method for titanate nanomaterials modification, and the developed novel CQDs/K2Ti6O13 hybrid material is promising for potential application on antibiotics removal from water and wastewater.
Liu X, Ji H, Li S, Liu W. Graphene modified anatase/titanate nanosheets with enhanced photocatalytic activity for efficient degradation of sulfamethazine under simulated solar light. Chemosphere [Internet]. 2019;233:198 - 206. 访问链接Abstract
Graphene modified anatase/titanate nanosheets (G/A/TNS) synthesized through hydrothermal treatment were used for solar-light-driven photocatalytic degradation of a typical pharmaceutically active compound, sulfamethazine (SMT). The optimal material was synthesized with 0.5 wt% of graphene loading (G/A/TNS-0.5), which could efficiently degrade 96.1% of SMT at 4 h. G/A/TNS-0.5 showed enhanced photocatalytic activity compared with the neat anatase and unmodified anatase/titanate nanosheets (A/TNS). UV–vis diffuse reflection spectra indicated that G/A/TNS-0.5 had a lower energy band gap (Eg) of 2.8 eV than A/TNS (3.1 eV). The grafted graphene acted as an electron transfer mediator after photoexcitation, resulting in inhibition on rapid recombination of electron-hole pairs. More importantly, architecture of graphene and titanate nanosheets both with two-dimensional structures greatly facilitated the photoexcited electron transfer. •OH and 1O2 were the primary reactive oxygen species (ROS) to SMT degradation. Fukui index (f -) derived from density functional theory (DFT) calculation predicted the active sites on SMT molecule, and then SMT degradation pathway was proposed by means of intermediates identification and theoretical calculation. Furthermore, G/A/TNS-0.5 could be well reused and 90.5% of SMT was also degraded after five runs. The developed new photocatalysts show great potential for degradation of emerging organic contaminants through photocatalysis under solar light.
Li M, Liu F, Ma Z, Liu W, Liang J, Tong M. Different mechanisms for E. coli disinfection and BPA degradation by CeO2-AgI under visible light irradiation. Chemical Engineering Journal [Internet]. 2019;371:750 - 758. 访问链接Abstract
CeO2-AgI, synthesized via depositing AgI nanoparticles onto CeO2 nanorods, was utilized for bacterial disinfection and organic contaminant degradation. Escherichia coli (E. coli) and Bisphenol A (BPA) were used as the model bacteria and emerging organic contaminant to test the photocatalytic activity of CeO2-AgI, respectively. Results showed that CeO2-AgI with the optimal AgI content exhibited superior photocatalytic activity over pure CeO2 or AgI for both inactivation of E. coli cells and BPA removal. However, the photocatalytic mechanisms for E. coli inactivation and BPA degradation were different. Specifically, the photo-generated holes (h+), photo-generated electrons (e−) and superoxide radicals (O2−) were the dominated active species for E. coli inactivation, whereas, BPA degradation relied on the generation of O2− and e−. Cell membrane disruption was found to be the main disinfection mechanism. The decomposition of BPA was clarified by detecting the degradation intermediates by LC–MS and DFT calculation. The facile synthesized CeO2-AgI exhibited good photocatalytic stability in four reused cycles and thus could be potentially applied to purify water.
Lin Y, Ma J, Liu W, Li Z, He K. Efficient removal of dyes from dyeing wastewater by powder activated charcoal/titanate nanotube nanocomposites: adsorption and photoregeneration. Environmental Science and Pollution Research [Internet]. 2019;26:10263–10273. 访问链接Abstract
Effective removal of dyes has been widely investigated by the adsorption of powder activated carbon and photodegradation by titanate nanotubes (TNTs). In this study, a facile one-step alkaline-hydrothermal method was applied to synthesize powder activated charcoal–supported TNTs (TNTs@PAC). Adsorption of three representative dyes, i.e., cationic methylene blue (MB), cationic rhodamine B (RhB), and anionic methyl orange (MO), onto TNTs@PAC was evaluated by the adsorption kinetic experiments and adsorption isotherms. The first 30 min is the main time phase of adsorption, and MB, RhB, and MO obtained the experimental equilibrium uptake of 173.30, 115.06, and 106.85 mg/g, respectively, indicating their final removal efficiencies of 100%, 69.36%, and 64.11%, respectively. The increase of pH value reduced adsorption capacity of MO (from 149.35 mg/g at pH of 2 to 96.99 mg/g at pH of 10), but facilitated MB adsorption, which was attributed to the charge distribution on the surface of TNTs@PAC and the charge of dyes at different pH. Furthermore, good capacity recoveries of MB by TNTs@PAC (>þinspace}99%) were observed after UV irradiation treatment, indicating the used TNTs@PAC can be easily recycled for the adsorption of MB by UV irradiation. Overall, TNTs@PAC is an effective process for remediation of dye-contaminated water because of its adsorption performance for all selected dyes and good regeneration capacity for MB.
Wang X, Liu W, Fu H, Yi X-H, Wang P, Zhao C, Wang C-C, Zheng W. Simultaneous Cr(VI) reduction and Cr(III) removal of bifunctional MOF/Titanate nanotube composites. Environmental Pollution [Internet]. 2019;249:502 - 511. 访问链接Abstract
Abstract: In this study, a series of BUC-21/titanate nanotube (BT-X) composites were facilely fabricated via ball-milling of 2-dimensional (2D) metal-organic framework (MOF) BUC-21 and titanate nanotubes (TNTs). The BT-X composites were characterized by powder X-ray diffraction (PXRD), Fourier transform infrared spectroscopy (FTIR), transmission electron microscopy (TEM), UV–visible diffuse-reflectance spectroscopy (UV–vis DRS), X-ray photoelectron spectrometer (XPS) and high resolution transmission electron microscopy (HRTEM). Both the photocatalytic reduction from Cr(VI) to Cr(III) and adsorptive removal of formed Cr(III) of BT-X composites were systematically investigated under different conditions including pH values and co-existing inorganic ions. It was found that BUC-21 (100 mg)/TNTs (100 mg) (BT-1) composites demonstrate remarkable ability of photocatalytic Cr(VI) reduction and adsorptive Cr(III) removal, as well as good reusability and stability. It is believed that the introduction of TNTs could capture the formed Cr(III) from the surface of BUC-21, which provided more active sites exposed to enhance the Cr(VI) reduction.
Chen X, You M, Wei J, Ke Y, Liu W, Sun W. Carbon nanotubes affect the formation of trihalomethanes during chlorination of bisphenol A. Chemical Engineering Journal [Internet]. 2019;370:337 - 345. 访问链接Abstract
Carbon nanotubes (CNTs) and trace contaminants often co-occur in natural waters and wastewaters, and they may become the precursors of disinfection byproducts (DBPs). However, the effects of CNTs on the formation of DBPs during chlorination of co-existed organic pollutants are unknown. This study compared the effects of three types of CNTs on the formation of DBPs during chlorination of bisphenol A (BPA). The results showed that, compared with the single system of BPA, CNTs significantly decreased the initial rate (Ri) and the second-order rate constant (k) of trihalomethanes (THMs) formation in the binary systems of CNTs and BPA. For example, Ri for the binary system (38.7–49.6 µg/(L·h)) was much lower than that for the single system of BPA (63.1 µg/(L·h)). Furthermore, the suppression effects depended not only on the type but also on the concentration of CNTs: the suppression of Ri and k by CNTs followed the order of pristine CNTs > hydroxyl CNTs > carboxylic CNTs, and increased with rising concentration of CNTs. The adsorption experiments and density functional theory (DFT) calculation further revealed that higher adsorption and stronger binding of BPA to CNTs resulted in greater suppression degree of Ri and k by CNTs.
Wu Q, Du Y, Huang Z, Gu J, Leung JYS, Mai B, Xiao T, Liu W, Fu J. Vertical profile of soil/sediment pollution and microbial community change by e-waste recycling operation. Science of The Total Environment [Internet]. 2019;669:1001 - 1010. 访问链接Abstract
The present study aims to assess the effect of electronic waste (e-waste) recycling on microbial community and the underlying modulation mechanism. Core soil/sediment samples were collected from an abandoned e-waste burning site and neighboring farmland/stream sites in Guiyu, China. High concentrations and health risks of toxic heavy metals, particularly, Sb and Sn, and halogenated flame retardants (HFRs), including decabromodiphenyl ether (BDE 209) and decabromodiphenyl ethane (DBDPE) were mostly retained at the top surface layers of soils/sediments (0–30 cm) after more than one year of natural vertical diffusion and microbe-facilitated biodegradation. Heavy metals, such as Ag, Cd, Cu, Pb, Sb, and Sn, played a critical role for the reduction of microbial diversity. This is the first study reporting the open burning of e-waste caused an obvious heat effect and enriched thermophilic/mesophilic microbes in local area. The acid washing during e-waste recycling process may result in the enrichment of acidophilic microbes. This investigation showed that e-waste processing operation resulted in not only severe pollution of the soils/sediments by various pollutants, but also reduction of microbial diversity that was difficult to self-store by the local ecosystem.
Zheng M, Zhou N, Liu S, Dang C, Liu Y, He S, Zhao Y, Liu W, Wang X. N2O and NO emission from a biological aerated filter treating coking wastewater: Main source and microbial community. Journal of Cleaner Production [Internet]. 2019;213:365 - 374. 访问链接Abstract
Nitrous oxide (N2O) and nitric oxide (NO) emissions from domestic wastewater treatment had been widely investigated due to their severe greenhouse effect and stratospheric ozone depletion. Researches concerning N2O and NO emissions from industrial wastewater treatment which usually contain high concentrations of nitrogen and refractory organics were still limited. In this study, N2O and NO emissions from a biological aerated filter (BAF) for coking wastewater treatment were investigated that achieved efficient nitrogen and chemical oxygen demand (COD) removal efficiency through short-cut nitrification and denitrification. Notably, emission factor of N2O and NO reached 23.58% and 0.09% respectively, much higher than those emitted from most domestic wastewater treatment plants. Moreover, batch experiments revealed that nitrifier denitrification contributed as high as 97.17% and 93.89% of the total generated N2O and NO, which was supposed to be the main source of green-house gases (GHGs) during coking wastewater treatment. The inhibition of denitrifying reductase by the toxic components in coking wastewater and the severe nitrite accumulations were key factors promoting the high emission of N2O and NO. Microbial community analysis based on high throughput sequencing of 16S rRNA gene revealed that ammonia-oxidizing bacteria and denitrifying bacteria distributed abundantly in the BAF reactor, while nitrite-oxidizing bacteria was almost absent. The huge imbalance between NO and N2O reductase was an underlying explanation for the high N2O emission in the present coking wastewater treatment according to Phylogenetic Investigation of Communities by Reconstruction of Unobserved States (PICRUSt) result. This study is of great significance to understanding the high N2O and NO emission and developing the control strategy when treating industrial wastewater with high-strength nitrogen and refractory organics.
Duan J, Ji H, Liu W, Zhao X, Han B, Tian S, Zhao D. Enhanced immobilization of U(VI) using a new type of FeS-modified Fe0 core-shell particles. Chemical Engineering Journal [Internet]. 2019;359:1617 - 1628. 访问链接Abstract
Sulfur-modified zero valent iron (S-ZVI) particles have been reported to show improved reactivity and selectivity than conventional ZVI. However, current methods for ZVI sulfidation do not fully utilize the advantages of the material, and S-ZVI has not been tested for U(VI) immobilization. In this work, we synthesized a new type of FeS-modified ZVI core-shell particles (FeS@Fe0) through a facile two-step reaction approach, and then tested for reductive sequestration of U(VI) in water. X-ray diffraction, Scanning transmission electron microscopy, and physical property analyses confirmed the formation of the core-shell structure, surface compositions and magnetic properties. Batch kinetic tests showed that FeS@Fe0 with an Fe0/FeS molar ratio of 1:1 offered the highest U(VI) reduction rate, prolonged reactive life than pristine ZVI, and the reduced uranium was most resistant to re-oxidation when exposed to oxygen. The retarded first-order kinetic model was able to adequately interpret the experimental rate data. FeS@Fe0 performed well over the pH range 5.5–9.0, with higher pH more favoring the reaction. High concentrations (5–10 mg/L) of humic acid, bicarbonate (1–5 mM) and Ca2+ (1 mM) showed only modest inhibition to the U(VI) reduction. Fourier transform infrared spectroscopy, X-ray photoelectron spectroscopy, and extraction studies indicated that U(VI) was immobilized via both direct adsorption and reductive precipitation, where Fe0 was the main electron source, with Fe0, sorbed Fe(II) and structural Fe(II) acting as the electron donors. FeS@Fe0 may serve as an improved material for efficient immobilization of U(VI) and other redox-active contaminants in water.
Liu W, Li Y, Liu F, Jiang W, Zhang D, Liang J. Visible-light-driven photocatalytic degradation of diclofenac by carbon quantum dots modified porous g-C3N4: Mechanisms, degradation pathway and DFT calculation. Water Research [Internet]. 2019;150:431 - 441. 访问链接Abstract
Metal-free photocatalysts have attracted growing concern in recent years. In this work, a new class of carbon quantum dots (CQDs) modified porous graphitic carbon nitride (g-C3N4) is synthesized via a facile polymerization method. With the optimal CQDs loading, the CQDs modified g-C3N4 exhibits ∼15 times higher degradation kinetic towards diclofenac (DCF) than that of pure g-C3N4. The enhanced photocatalytic activity can be ascribed to the improved separation of charge carriers as well as the tuned band structure. Moreover, a photosensitation-like mechanism is proposed to elucidate the photo-generated electrons transfer and reactive radicals formation. CQDs are anchored to g-C3N4 surface via CO bond, which provide channels for the preferential transfer of photo-excited electrons on DCF molecule to the conduction band of g-C3N4. Superoxide radical (·O2−) dominates the degradation of DCF, while holes (h+) show a negligible contribution. Density functional theory (DFT) calculation successfully predicts that the sites on DCF molecule with high Fukui index (f0) are preferable to be attacked by radicals. DCF degradation pathway mainly includes ring hydroxylation, ring closure and CN bond cleavage processes. Acute toxicity estimation indicates the formation of less toxic intermediates/products compared to DCF after photocatalysis. Moreover, the hybrid photocatalysts exhibit good reusability in five consecutive cycles. This work not only proposes a deep insight into photosensitation-like mechanism in the photocatalysis system by using C3N4-based materials, but also develops new photocatalysts for potential application on removal of emerging organic pollutants from waters and wastewaters.
Liu F, Liang J, Chen L, Tong M, Liu W. Photocatalytic removal of diclofenac by Ti doped BiOI microspheres under visible light irradiation: Kinetics, mechanism, and pathways. Journal of Molecular Liquids [Internet]. 2019;275:807 - 814. 访问链接Abstract
BiOI microspheres doped with different amounts of Ti were fabricated and used to remove diclofenac (DCF) from water under visible light irradiation. The fabricated photocatalysts were well characterized. Ti doped BiOI microspheres were found to exhibit higher photocatalytic activity towards DCF under visible light compared with BiOI. Ti doping broadened the band gap of BiOI, which leads to a more negative conduction band edge and a higher reducing activity of photo-generated electrons, thus facilitates ·O2− production during photocatalysis. Among all the fabricated Ti doped BiOI microspheres, TB450 exhibited the highest DCF photocatalytic removal efficiency. Specifically, 99.2% of DCF (C0 = 10 mg L−1) was removed by TB450 (250 mg L−1) at pH 5 within 90 min under visible light irradiation. Scavenger experiments indicated that active species including h+, ·O2− and H2O2 played important roles in the photocatalytic process. The degradation pathway of DCF was elucidated by theoretical density functional theory (DFT) and by-products identification through liquid chromatograph mass spectrometer (LC-MS) analysis. DCF degradation pathway mainly included hydroxylation and the cleavage of CN bond. DFT calculation can well interpret the degradation mechanism and the sites of DCF molecule with high radical-attack Fukui index (f0) exhibit high reactivity. Acidic condition was found to facilitate the DCF photocatalytic removal. Due to strong photo-stability, Ti doped BiOI microspheres contained good visible-light-driven (VLD) photocatalytic removal efficiency for DCF in the fourth consecutive reused cycle. Ti doped BiOI microspheres can be employed as a cost-effective and high-efficient material to efficiently degrade emerging contaminants (e.g., pharmaceutical) from wastewaters under visible light conditions.
Ji H, Zhu Y, Liu W, Bozack MJ, Qian T, Zhao D. Sequestration of pertechnetate using carboxymethyl cellulose stabilized FeS nanoparticles: Effectiveness and mechanisms. Colloids and Surfaces A: Physicochemical and Engineering Aspects [Internet]. 2019;561:373 - 380. 访问链接Abstract
Technetium (99Tc) typically exists as pertechnetate (TcO4−) and hydrated oxide (TcO2·nH2O) in soil and groundwater. While the former, Tc(VII), is very soluble and mobile in the environment, the latter is considered sparingly soluble and immobile. Consequently, immobilization of Tc(VII) can be achieved through conversion of Tc(VII) into Tc(IV). In this study, carboxymethyl cellulose (CMC) stabilized FeS nanoparticles (CMC-FeS) were prepared and tested for reductive immobilization of Tc(VII). Effects of nanoparticle dosage and water chemistry, including pH, humic acid and Ca2+ ions, were examined. At a dosage of 100 mg/L of CMC-FeS as Fe, CMC-FeS rapidly removed >96% of 1.2 μM of Tc(VII) within 1 h, with a retarded first-order rate constant (ka) of 150.32 h-1. Higher pH in the range of 5.0–9.0 favored the reaction, with an optimal pH range of 8.0–9.0. While Ca2+ (up to 2 mM) only modestly affected the Tc(VII) removal, high concentrations of humic acid (up to 10 mg/L as TOC) showed increased inhibition on the Tc(VII) removal rate. FTIR and XPS analyses indicated that CMC-FeS immobilized TcO4− through reductive conversion of TcO4− into TcO2(s) and formation of Tc2S7 precipitate. The immobilized Tc remained insoluble when aged for 100 days under anoxic conditions, whereas up to 22.9% of the immobilized Tc was remobilized when it was exposed to air for 100 days.

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