REMOVAL OF ORGANIC POLLUTANTS USING TITANIUM DIOXIDE MEDIATED PHOTOCATALYTIC OXIDATION

A simple and effective method of removing polluted organics in water is reported here.Titanium dioxide is a catalyst in photo-oxidation of monocrotophos.The mechanism of photocatalytic oxidation and the kinetics of the reaction were studied. This same principle also leads to the construction of instrument of PTR-FIA analysis for monitoring organic phosphorus and phosphate in water.

Solar Oxidation and Removal of Arsenic from Groundwater Utilizing a Semicircular Section Tubular Photoreactor

A semicircular section tubular photoreactor has been constructed, characterized and applied to the treatment of groundwater contaminated with As（V） by means of the SORAS （solar oxidation and removal of arsenic） technique, using ferrous and citrate salts. The solar concentrator was built with recyclable waste materials： glass tubes from fluorescent lamps and 6-inch diameter PVC pipes cut in half and covered by aluminum foil. The reactor concentrates solar radiation up to 2.8 times its natural intensity. Batch irradiation experiments followed by controlled agitation （shear rate = 30-33 s^-1; 20 min agitation period） showed that the photoreactor accelerates the formation of settleable floccules （Dp 〉 0.5mm）, compared with a fluorescent lamp glass tube alone and a 2 L PET （polyethylene terephthalate） bottle. Irradiation times necessary for floccule formation in the photoreactor, the fluorescent lamp tube and the PET bottle were 15 min, 25 min and 60 min, respectively. Continuous flow experiments using a photoreactor with a photo-collection area of 0.9 m^2 and a hydraulic retention time （equal to the irradiation time） of 15 rain showed that immediate formation of floccules of good settleability occurs when the solution is subjected to moderate agitation （33 s^-1）. An efficiency of 98.36% for As（V） removal was obtained with a final concentration of 16.5 ktg/L in decanted waters. In accordance to these results, the photoreactor is able to treat approximately 130 L/m^2 within a 5-h period with UVA irradiation intensities of 50-70 W/mE.

Heterostructured BiOI@La(OH)_3 nanorods with enhanced visible light photocatalytic NO removal

Heterostructured BiOI@La（OH）3 nanorod photocatalysts were prepared by a facile chemical impregnation method.The enhanced visible light absorption and charge carrier separation can be simultaneously realized after the introduction of BiOI particles into La（OH）3 nanorods.The BiOI@La（OH）3 composites were applied for visible light photocatalytic oxidization of NO in air and exhibited an enhanced activity compared with BiOI and pure La（OH）3 nanorods.The results show that the energy levels between the La（OH）3 and BiOI phases matched well with each other,thus forming a heterojunctioned BiOI@La（OH）3 structure.This band structure matching could promote the separation and transfer of photoinduced electron-hole pairs at the interface,resulting in enhanced photocatalytic performance under visible light irradiation.The photocatalytic performance of BiOI@La（OH）3 is shown to be dependent on the mass ratio of BiOI to La（OH）3.The highest photocatalytic performance can be achieved when the mass ratio of BiOI to La（OH）3 is controlled at 1.5.A further increase of the mass ratio of BiOI weakened the redox abilities of the photogenerated charge carriers.A new photocatalytic mechanism for BiOI@La（OH）3 heterostructures is proposed,which is directly related to the efficient separation of photogenerated charge carriers by the heterojunction.Importantly,the as-prepared BiOI@La（OH）3 heterostructures exhibited a high photochemical stability after multiple reaction runs.Our findings demonstrate that BiOI is an effective component for the formation of a heterostructure with the properties of a wide bandgap semiconductor,which is of great importance for extending the light absorption and photocatalytic activity of wide bandgap semiconductors into visible light region.

Solvent-assisted synthesis of porous g-C_3N_4 with efficient visible-light photocatalvtic performance for NO removal

Graphitic carbon nitride（g-C3N4） with efficient photocatalytic activity was synthesized through thermal polymerization of thiourea with the addition of water（CN-W） or ethanol（CN-E） at 550 ℃for 2 h.The physicochemical properties of the g-C3N4 were investigated by X-ray diffraction,transmission electron microscopy,ultraviolet-visible spectroscopy,photoluminescence spectroscopy,diffuse-reflection spectroscopy,BET and BJH surface area characterization,and elemental analysis.The carbon content was found to have self-doped into the g-C3N4 matrix during the thermal polymerization of thiourea and ethanol.CN-W and CN-E showed considerably enhanced visible-light photocatalytic activity,with NO removal percentages of 37.2%and 48.3%,respectively.Compared with pure g-C3N4,both the short and long lifetimes of the charge carriers in CN-W and CN-E were found to be prolonged.The mechanism of improved visible-light photocatalytic activity was deduced.The present work may provide a facile route to optimize the microstructure of g-C3N4photocatalysts for high-performance environmental and energy applications.

Investigation of NO removal using a pulseassisted RF discharge

In this paper,removal of nitrogen oxide（NO） is investigated in capacitive atmospheric pressure discharges driven by both radio-frequency（RF） and trapezoidal pulsed power with a onedimensional self-consistent fluid model.The results show that the number density of NO could be reduced significantly once a short pulse of low duty ratio is additionally applied to the RF power.It is found that the process of NO removal by the pulse-modulated RF discharge could be divided into three stages：the quick reaction stage,the NO removal stage,and the sustaining stage.Furthermore,the temporal evolution of particle densities is analyzed,and the key reactions in each stage are discovered.Finally,the influence on the removal efficiency of the voltage amplitude of the pulse and the RF voltage amplitude is investigated.

Introducing oxygen vacancies in TiO_(2) lattice through trivalent iron to enhance the photocatalytic removal of indoor NO

The synthesis of oxygen vacancies(OVs)-modified TiO_(2)under mild conditions is attractive.In this work,OVs were easily introduced in TiO_(2)lattice during the hydrothermal doping process of trivalent iron ions.Theoretical calculations based on a novel charge-compensation structure model were employed with experimental methods to reveal the intrinsic photocatalytic mechanism of Fe-doped TiO_(2)(Fe-TiO_(2)).The OVs formation energy in Fe-TiO_(2)(1.12 eV)was only 23.6%of that in TiO_(2)(4.74 eV),explaining why Fe^(3+)doping could introduce OVs in the TiO_(2)lattice.The calculation results also indicated that impurity states introduced by Fe^(3+)and OVs enhanced the light absorption activity of TiO_(2).Additionally,charge carrier transport was investigated through the carrier lifetime and relative mass.The carrier lifetime of Fe-TiO_(2)(4.00,4.10,and 3.34 ns for 1at%,2at%,and 3at%doping contents,respectively)was longer than that of undoped TiO_(2)(3.22 ns),indicating that Fe^(3+) and OVs could promote charge carrier separation,which can be attributed to the larger relative effective mass of electrons and holes.Herein,Fe-TiO_(2)has higher photocatalytic indoor NO removal activity compared with other photocatalysts because it has strong light absorption activity and high carrier separation efficiency.

Ternary Ag/AgCl/BiOIO_3 composites for enhanced visible-light-driven photocatalysis

Ternary Ag/AgC l/BiO IO3 composite photocatalysts are prepared by a facile method. Enhanced visible-light absorption and charge carrier separation are achieved after the introduction of Ag/AgC l particles into BiO IO3 systems,as revealed by ultraviolet-visible diffuse-reflectance spectrometry,photocurrent response and electrochemical impedance spectroscopy. The Ag/AgC l/BiO IO3 composites are applied to the visible-light photocatalytic oxidization of NO in air and exhibit an enhanced activity for NO removal in comparison with Ag/AgC l and pure BiO IO3. A possible photocatalytic mechanism for Ag/AgC l/BiO IO3 is proposed,which is related to the surface plasmon resonance effects of Ag metal and the effective carrier separation ability of BiO IO3. This work provides insight into the design and preparation of BiO IO3-based materials with enhanced visible-light photocatalysis ability.

NO reduction by CO over TiO_2-γ-Al_2O_3 supported In/Ag catalyst under lean burn conditions

TiO2/γ-Al2O3 supported In/Ag catalysts were prepared by impregnation method,and investigated for NO reduction with CO as the reducing agent under lean burn conditions.The microscopic structure and surface properties of the catalysts were studied by N2 adsorption-desorption,X-ray diffraction,transmission electron microscopy,X-ray photoelectron spectroscopy,ultraviolet-visible spectroscopy,H2 temperature-programmed reduction and Fourier transform infrared spectroscopy.TiO2/γ-Al2O3 supported In/Ag is a good catalyst for the reduction of NO to N2.It displayed high dispersion,large amounts of surface active components and high NO adsorption capacity,which gave good catalytic performance and stability for the reduction of NO with CO under lean burn conditions.The silver species stabilized and improved the dispersion of the indium species.The introduction of TiO2 into the γ-Al2O3 support promoted NO adsorption and improved the dispersion of the indium species and silver species.

Microspheres of graphene oxide coupled to N-doped Bi_2O_2CO_3 for visible light photocatalysis

Hierarchical microspheres of a graphene oxide（GO） coupled to N‐doped（BiO）2CO3 composite（N‐BOC‐GO） was synthesized by a simple hydrothermal approach. The N‐BOC‐GO composite gave enhancement in photocatalytic activity compared to the pure BOC and N‐BOC samples. With 1.0wt% GO, 62% NO removal was obtained with N‐BOC‐GO. The factors enhancing the photocatalytic performance were the high electron‐withdrawing ability and high conductivity of GO and improved visible light‐harvesting ability of N‐BOC‐GO with a 3D hierarchical architecture due to the surface scattering and reflecting（SSR） effect. An effective charge transfer from N‐BOC to GO was demonstrated by the much weakened photoluminescene intensity of the N‐BOC‐GO composite. This work highlights the potential application of GO‐based photocatalysts in air purification.

Enhanced plasmonic photocatalysis by SiO_2@Bi microspheres with hot-electron transportation channels via Bi–O–Si linkages

The semimetal Bi has received increasing interest as an alternative to noble metals for use in plasmonic photocatalysis. To enhance the photocatalytic efficiency of metallic Bi, Bi microspheres modified by SiO2 nanoparticles were fabricated by a facile method. Bi-O-Si bonds were formed between Bi and SiO2, and acted as a transportation channel for hot electrons. The SiO2@Bi microspheres exhibited an enhanced plasmon-mediated photocatalytic activity for the removal of NO in air under 280 nm light irradiation, as a result of the enlarged specific surface areas and the promotion of electron transfer via the Bi-O-Si bonds. The reaction mechanism of photocatalytic oxidation of NO by SiO2@Bi was revealed with electron spin resonance and in situ diffuse reflectance infrared Fourier transform spectroscopy experiments, and involved the chain reaction NO -> NO2 -> NO3- with center dot OH and center dot O-2(-) radicals as the main reactive species. The present work could provide new insights into the in-depth mechanistic understanding of Bi plasmonic photocatalysis and the design of high-performance Bi-based photocatalysts. (C) 2017, Dalian Institute of Chemical Physics, Chinese Academy of Sciences. Published by Elsevier B.V. All rights reserved.

Influence of sulfation on CeO_2-ZrO_2 catalysts for NO reduction with NH_3

CeO2‐ZrO2 (CeZr) and sulfated CeO2‐ZrO2 (S‐CeZr) catalysts were prepared for the selective catalytic reduction of NO with NH3. The CeZr catalysts exhibited higher activity at low temperatures (< 200°C) and lower activity at high temperatures (> 200 °C) than the S‐CeZr catalysts. The sulfation ofCeZr was studied in terms of surface acidity, redox properties and NO adsorption‐desorption bytemperature‐dependent experiments and in situ infrared spectroscopy. S‐CeZr displayed high concentrationsof acidic sites and increased surface acidities, but poor reducibility compared with CeZr.The high acidity of S‐CeZr was attributed to the presence of Br?nsted acid sites, arising mainly fromthe surface sulfates. Because the surface was covered with sulfate species, S‐CeZr showed lower NOadsorption and weaker oxidation ability than CeZr. The adsorption of NH3 on the Br?nsted acid sites restricted the reaction with NO at low temperatures, but the selective catalytic reduction cycle occurred easily at relatively low temperatures (150 °C), and the weakly bound nitrite was partially activated on the S‐CeZr catalyst at relatively high temperatures (300 °C). The catalytic mechanisms for the CeZr and S‐CeZr catalysts at 150 and 300 °C were also studied.

Evolution mechanism of active sites for selective catalytic reduction of NO_(x) with NH_(3) over Fe-ZSM-5 catalysts doped by Ce/Cu

Fe-ZSM-5 catalysts modified by Cu and Ce by aqueous solution ion-exchange and incipient wetness impregnation methods were tested in the selective catalytic reduction of NO_(x) with NH_(3).A variety of characterization techniques(NH_(3)-SCO,BET,XRD,XPS,UV-Vis,NH_(3)-TPD,H_(2)-TPR)were used to explore the changes of the active sites,acid sites and pore structure of the catalyst.It was found that the dispersion of active Cu species and Fe species had great influences on the catalytic activity in the whole catalytic process.The Cu doping into the Fe-ZSM-5 catalyst produced new active species,isolated Cu ions and CuO particles,resulting in the improved low-temperature catalytic activity.However,the NH_(3) oxidation was enhanced,and part of the Fe^(3+)active sites and more Brønsted acidic sites in the catalyst were occupied by Cu species,which causes the decrease of the high-temperature activity.The recovery of hightemperature activity could be attributed to the recovery of active Cu species and Fe species promoted by Ce and the promotion of active species dispersion.The results provide theoretical support for adjusting the active window of Febased SCR catalyst by multi-metal doping.

Synergistic catalytic removals of NO,CO and HC over CeO_2 modified Mn-Mo-W-O_x/TiO_2-SiO_2 catalyst

A series of Mn-Mo-W-O_x/TiO_2-SiO_2 catalysts was modified with CeO_2 using an extrusion molding method. The catalytic activities of the obtained catalysts were tested for the synergistic catalytic removals of CO, NO and C_3H_8. The ratio of catalyst composition on catalytic activities for NH_3-SCR was optimized, which reveals that the molar ratio of Ti/Si was 9：1 and the catalyst containing 1.5 wt% CeO_2 and 12 wt% Mn-Mo-W-O_x exhibits the best catalytic performances. These samples were characterized by XRD, N_2-BET, Py-IR, NH_3-TPD, SEM/element mapping, H_2-TPR and XPS, respectively. Results show that the optimal catalyst exhibits more than 99% NO conversion, 86% CO conversion and 100% C_3H_8 conversion under GHSV of 5000 h^（-1）. In addition, the GHSV has little influence on removal of NO when it is less than 15,000 h^（-1）. Furthermore, the addition of CeO_2 will enhance the surface acidity, increase Mn^（4＋）concentration and inhibit the grain growth, which are favorable for the excellent catalytic performance.Anyway,the 1.5 wt% CeO_2-12 wt% Mn-Mo-W-O_x/TiO_2-SiO_2 possesses outstanding redox properties,abundant acid sites and high Mn^（4＋） concentration, which provide a guarantee for synergistic catalytic removal of CO, NO and HC.

Efficient removal of phosphate from aqueous solution using novel magnetic nanocomposites with Fe_3O_4@SiO_2 core and mesoporous CeO_2 shell

Fe_3O_4@SiO_2 magnetic nanoparticles functionalized with mesoporous cerium oxide（Fe_3O_4@SiO_2@mCeO_2） was fabricated as a novel adsorbent to remove phosphate from water. The prepared adsorbent was characterized by X-ray diffractometry（XRD）, transmission electron microscopy（TEM）, nitrogen adsorption-desorption and vibrating sample magnetometry（VSM）, and its phosphate removal performance was investigated through the batch adsorption studies. Characterization results confirmed that mesoporous cerium oxide was successfully assembled on the surface of Fe_3O_4@SiO_2 nanoparticles, and the synthesized adsorbent possessed a typical core-shell structure with a BET surface area of 195 m^2/g, accessible mesopores of 2.6 nm, and the saturation magnetization of 21.11 emu/g. The newly developed adsorbent had an excellent performance in adsorbing phosphate, and its maximum adsorption capacity calculated from the Langmuir model was 64.07 mg/g. The adsorption was fast, and the kinetic data could be best fitted with the pseudo-second-order kinetic model. The phosphate removal decreased with the increase of solution pH（2 to 10）, while the higher ionic strength slightly promoted the phosphate adsorption. The presence of Cl~– and SO^（2–）_4 could enhance the adsorption of phosphate whereas HCO~–_ 3 had interfering effect on the phosphate adsorption. The adsorption mechanism was studied by analyzing Zeta potential and FTIR spectroscopy, and the results indicated that the replacement of the surface hydroxyl groups by phosphate ions with the formation of inner-sphere complex played a key role in the phosphate adsorption. The spent adsorbent could be quickly separated from aqueous solution with the assistance of the external magnetic field, and the adsorbed phosphate could be effectively desorbed using a 1 mol/L NaOH solution.

Aerobic N_2O emission for activated sludge acclimated under different aeration rates in the multiple anoxic and aerobic process

Nitrous oxide（N_2O） is a potent greenhouse gas that can be emitted during biological nitrogen removal. N_2O emission was examined in a multiple anoxic and aerobic process at the aeration rates of 600 m L/min sequencing batch reactor（SBRL） and 1200 m L/min（SBRH）.The nitrogen removal percentage was 89% in SBRLand 71% in SBRH, respectively. N_2O emission mainly occurred during the aerobic phase, and the N_2O emission factor was 10.1%in SBRLand 2.3% in SBRH, respectively. In all batch experiments, the N_2O emission potential was high in SBRLcompared with SBRH. In SBRL, with increasing aeration rates, the N_2O emission factor decreased during nitrification, while it increased during denitrification and simultaneous nitrification and denitrification（SND）. By contrast, in SBRHthe N_2O emission factor during nitrification, denitrification and SND was relatively low and changed little with increasing aeration rates. The microbial competition affected the N_2O emission during biological nitrogen removal.

Nb_2O_5 nanowires in-situ grown on carbon fiber: A high-efficiency material for the photocatalytic reduction of Cr(Ⅵ)

Niobium oxide nanowire-deposited carbon fiber（CF） samples were prepared using a hydrothermal method with amorphous Nb2O5·nH2O as precursor. The physical properties of the samples were characterized by means of numerous techniques, including X-ray diffraction（XRD）, energy-dispersive spectroscopy（EDS）, scanning electron microscopy（SEM）, transmission electron microscopy（TEM）, selected-area electron diffraction（SAED）, UV–visible spectroscopy（UV–vis）, N2 adsorption–desorption, Fourier transform infrared spectroscopy（FT-IR）, and X-ray photoelectron spectroscopy. The efficiency for the removal of Cr（VI） was determined.Parameters such as pH value and initial Cr（VI） concentration could influence the Cr（VI） removal efficiency or adsorption capacity of the Nb2O5/carbon fiber sample obtained after hydrothermal treatment at 160°C for 14 hr. The maximal Cr（VI） adsorption capacity of the Nb2O5 nanowire/CF sample was 115 mg/g. This Nb2O5/CF sample also showed excellent photocatalytic activity and stability for the reduction of Cr（Ⅵ） under UV-light irradiation： the Cr（VI） removal efficiency reached 99.9% after UV-light irradiation for 1 hr and there was no significant decrease in photocatalytic performance after the use of the sample for 10 repeated cycles. Such excellent Cr（VI） adsorption capacity and photocatalytic performance was related to its high surface area,abundant surface hydroxyl groups, and good UV-light absorption ability.

Non-thermal plasma treatment of Radix aconiti wastewater generated by traditional Chinese medicine processing

The wastewater effluent from Radix aconiti processing, an important step in the production processes of traditional Chinese medicine（TCM）, is a type of toxic wastewater and difficult to treat. Plasma oxidation methods have emerged as feasible techniques for effective decomposition of toxic organic pollutants. This study examined the performance of a plasma reactor operated in a dielectric barrier discharge（DBD） to degrade the effluent from R. aconiti processing. The effects of treatment time, discharge voltage, initial pH value and the feeding gas for the reactor on the degradation of this TCM wastewater were investigated. A bacterium bioluminescence assay was adopted in this study to test the toxicity of the TCM wastewater after non-thermal plasma treatment. The degradation ratio of the main toxic component was 87.77% after 60 min treatment with oxygen used as feed gas and it was 99.59% when the initial p H value was 8.0. High discharge voltage and alkaline solution environment were beneficial for improving the degradation ratio. The treatment process was found to be capable of reducing the toxicity of the wastewater to a low level or even render it non-toxic. These experimental results suggested that the DBD plasma method may be a competitive technology for primary decomposition of biologically undegradable toxic organic pollutants in TCM wastewater.

Overestimate of remediation efficiency due to residual sodium persulfate in PAHs contaminated soil and a solution

Oxidation remediation is a commonly used technology for PAHs contaminated soil presently,but the overestimate of efficiency due to ongoing remediation by residual oxidants during extraction and testing has not been paid enough attention.In this study,persulfate was activated by Fe(Ⅱ)to investigate the effects of residual oxidants on PAHs removal during detection process and the elimination effects of adding Na_(2)SO_(3) and extending sampling time on residual oxidants.Results verified that the residual oxidants removed PAHs in extraction process,making the results lower than the actual values:the detection recovery rate η of ΣPAHs and 3-6 ring PAHs ranged from 24.3%(25%Na_(2)S_(2)O_(8)treatment)to 87.4%(5%Na_(2)S_(2)O_(8)+4/4Fe^(2+) treatment),20.1%-99.0%,28.9%-87.9%,20.8%-89.4%,and 1.8.6%-76.9%,respectively.After adding Na_(2)SO_(3),the accuracy of detection results increased significantly:the η of ΣPAHs and 3-6 ring PAHs increased to 64.1%-96.5%,58.8%-95.5%,73.8%-114.4%,60.6%-95.6%,and 45.4%-77.1%,respectively.After 49 days of adding oxidants,residual oxidants had no considerable effect on the detection of PAHs,indicating it was appropriate to start soil remediation verification sampling49 days after the remediation was completed.The observed results will help scientific evaluation of the remediation effects of chemical oxidation on or-ganic contaminated soil.