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1.

Introduction

Efficient immobilization of TiO2 nanoparticles on the surface of Mg2Al-LDH nanosheets was performed by delamination/restacking process.

Experimental part

The structural and textural properties of as-prepared nanocomposite were deeply analyzed using different solid-state characterization techniques such as: X-ray powder diffraction, Fourier transform infrared spectroscopy, and Raman spectroscopies, chemical analysis, X-ray photoelecton spectroscopy, N2 adsorption?Cdesorption, and electronic microscopy.

Results and discussion

The photocatalytic properties of immobilized TiO2 nanoparticles on Mg2Al were investigated using the photodegradation of two model pollutants: Orange II and 4-chlorophenol, and compared with pure colloidal TiO2 solution.

Conclusion

It appears that Orange II photodegradation was systematically faster and more efficient than 4-chlorophenol photodegradation regardless of the medium pH. Moreover under slightly basic conditions, even if the TiO2 photocatalytic efficiency decreases, photodegradation performed in presence of easily recovered TiO2/Mg2Al1.5 nanocomposite gives rise to comparable or better results than pure TiO2.  相似文献   

2.

Introduction

The photocatalytic degradation of Orange G (OG) dye has been investigated using synthesised nanocrystalline ZnO as a photocatalyst and sunlight as the irradiation source. The formation of ZnO prepared from its precursor was confirmed through FT-IR and powder X-ray diffraction analyses.

Materials and methods

Surface morphology was characterised by scanning electron microscope and transmission electron microscope analysis. Band gap energy of synthesised nanocrystalline ZnO was calculated using diffuse reflectance spectroscopy (DRS). Different experimental parameters such as effects of pH, dye concentrations and mass of catalyst were standardised in order to achieve complete degradation of the dye molecules under solar light irradiation.

Results

The kinetics of oxidation of OG was also studied. The complete degradation of OG was evident after 90 min of irradiation at an initial pH of 6.86. The degradation of OG was confirmed by UV?CVisible spectrophotometer, high-pressure liquid chromatography, ESI-Mass and chemical oxygen demand analyses.

Conclusion

The adsorption of dye onto catalytic surface was analysed employing model equations such as Langmuir and Freundlich isotherms, and it was found that the Langmuir isotherm model best fitted the adsorption data. The solar photodegradation of OG followed pseudo-first-order kinetics. HPLC and ESI-Mass analyses of the degraded samples suggested that the dye molecules were readily degraded under solar irradiation with nanocrystalline ZnO.  相似文献   

3.

Objective

This work aims to investigate the correlation between the photocatalytic activity determined by methylene blue bleaching (DIN 52980), stearic acid degradation, and degradation of acetone in gas phase.

Method

The photocatalytic TiO2 coatings included in this investigation ranged from thin commercially available coatings (ActivTM and BioCleanTM) and ready to use suspensions (Nano-X PK1245) to lab-produced PVD and sol?Cgel coatings. XRD analysis of the photocatalytic coatings showed that all the coatings consisted of nanocrystalline anatase, although the thickness and porosity varied considerably.

Results

The study showed that the reproducibility of the activity measurements was good. However, more importantly, the investigation showed that there is a good correlation between the activities determined by the different methods even though the characteristics of the photocatalytic coatings and the organic probe molecules varied considerably.

Conclusion

The overall findings of this work suggest that there is a good correlation between the investigated methods. These results are promising for the future work concerning standardization of methods for determination of the activity of photocatalytic films.  相似文献   

4.

Introduction

The removal of natural organic matter (NOM) from water is becoming increasingly important in order to prevent the formation of carcinogenic disinfection by-products. The inadequate removal of NOM has a bearing on the capacity of the other treatment processes to remove organic micro-pollutants or inorganic species that may be present in the water. New methods are therefore currently being sought to effectively characterise NOM and also to ensure that it is sufficiently removed from drinking water sources.

Methodology

Nitrogen- and palladium-co-doped TiO2 was synthesised by a modified sol?Cgel method and evaluated for its photocatalytic degradation activity on NOM fractions under simulated solar radiation. The photocatalyst was characterised by FT-IR, Raman, XRD, DRUV?Cvis, SEM, TEM, EDS, XPS and TGA. FT-IR confirmed the presence of OH groups on thermally stable, nearly spherical anatase nanoparticles with an average diameter of 20?nm. PdO species appeared on the surface of the TiO2 as small uniformly dispersed particles (2 to 3?nm). A red shift in the absorption edge compared to commercial anatase TiO2 was confirmed by DRUV?Cvis. In order to gain a better insight into the response of NOM to photodegradation, the NOM was divided into three different fractions based on its chemical nature.

Results and discussion

Photodegradation efficiencies of 96, 38 and 15?% were realised for the hydrophobic, hydrophilic and transphilic NOM fractions, respectively. A reasonable mechanism was proposed to explain the photocatalytic degradation of the NOM fractions. The high photocatalytic activity could be attributed to the larger surface area, smaller crystalline size and synergistic effects of the co-dopants N and Pd in the TiO2 crystal.  相似文献   

5.
Photocatalytic properties of titanium (IV) oxide (TiO2) in anatase form can be used for various purposes, including photocatalytic purification of water. For such an application, suspended or fixed photocatalytic reactors are used. Those with fixed phase seem to be preferred due to some advantages, one of which is the avoidance of photocatalyst filtration. To avoid leaching and exfoliation of the fixed phase, an immobilization procedure leading to a good adhesion of a catalyst to a substrate is crucial. Within this work, we present physical and photocatalytic characterization results of five commercially available TiO2 photocatalysts (P25, P90, PC500, KRONOClean 7000, VPC-10) and one pigment (Hombitan LO-CR-S-M), which were successfully immobilized on glass slides by a “sol suspension” procedure. Different mechanical tests and characterization methods were used to evaluate the stability and morphology of the layers. Evaluation of photocatalytic activity was done by tests under UVA and UV–vis irradiation, using a method based on the detection of the fluorescent oxidation product of terephthalic acid (TPA), i.e., hydroxyterephthalic acid (HTPA). Aeroxide® P90 incorporated into the silica-titania binder was the most photocatalytically active layer and, unlike the others, showed significant increase of photocatalytic activity through the entire range of tested UVA irradiation intensities (2.3 mW/cm2–6.1 mW/cm2). The high mechanical stability of some photocatalytic layers allows using them in water photocatalytic purification reactions.  相似文献   

6.

Introduction

Solar wastewater treatment based on photocatalytic reactions is a green process that utilizes renewable energy resources and minimizes secondary pollution. Reactor design plays an important role in promoting treatment efficiency and throughput density (based on unit volume of the reactor).

Experimental

A rotating disk reactor that significantly increases the process efficiency has been designed and evaluated for application to photocatalytic decomposition of dye pollutants in aqueous solutions. In this process, a novel multi-layer rotating disk reactor (MLRDR) was presented. Photocatalyst (TiO2) particles are immobilized on the surfaces of disks. Within each layer of the reactor, methyl orange aqueous solution is allowed to flow from the center of the disk in a radial direction along the surface of the disk, which is rotating at high speed and is irradiated with UV lamps. The effluent is then directed to the center of another layer that lies underneath. Up to four stacked layers have been tested in this study, and the effects due to the number of the layers and volumetric flow rate on reaction conversion are investigated.

Results and discussion

The efficiency of this photocatalytic reactor exhibits complex dependence on these parameters. With selected operating conditions, conversions greater than 95% can be achieved within seconds of residence time. Design equations of the reactor have been derived based on fluid dynamics and kinetic models, and the simulation results show promising scale-up potential of the reactor.  相似文献   

7.

Introduction

Transition from first- to second-generation photocatalysts has followed the notion that greater absorption of light in the visible region would yield greater spectral sensitivity and greater photoactivity. Though a promising strategy, in practice, it did not meet expectation because of various side issues, which in many cases has led to loss of photoactivity and chemical reactivity. This article examines some earlier notions that arose from applications of different metal oxides (e.g., TiO2, ZnO, MgO among others) that made these oxides good photocatalysts in many processes.

Discussion

Phenomena that proved relevant in developing next generation photoactive materials are considered: the dependence of the activity of photocatalysts on the band gap energy, the spectral variations of the activity of photoactive materials, and the spectral variations of selectivity of photoactive materials. The tendency to decrease the energy of actinic photons through doping in forming second-generation photocatalysts is completely opposite the fundamental observation in first-generation photocatalysts whereby the activity increased with increasing band gap energy. Extension of spectral sensitivity of second-generation photoactive materials also caused a decrease of their photoactivity; hence, some notions are reconsidered to produce next(third) generation photoactive materials.

Summary

The article proposes the following concepts to develop next generation photocatalysts: (1) multi(two)-photon excitation of photoactive materials with lower energy photons to achieve the same excited state as with higher energy photons, (2) utilization of heterojunctions to drive electronic processes in the desired direction, and (3) selective photoexcitation of localized electronic states to gain better selectivity.  相似文献   

8.

Background, aim

The aims of the NORMACAT project are: to develop tools and unbiased standardized methods to measure the performance and to validate the safety of new materials and systems integrating photocatalysis, to develop new photocatalytic media with higher efficiency and to give recommendations aimed at improving the tested materials and systems.

Method

To achieve this objective, it was necessary to design standardized test benches and protocols to assess photocatalytic efficiency of materials or systems used in the treatment of volatile organic compounds (VOCs) and odour under conditions close to applications. The tests are based on the validation of robust analytical methods at the parts per billion by volume level that not only follow the disappearance of the initial VOCs but also identify the secondary species and calculate the mineralization rates.

Results

The first results of inter-laboratory closed chamber tests, according to XP B44-013 AFNOR standard, are described. The photocatalytic degradation of mixtures of several defined pollutants under controlled conditions (temperature, relative humidity, initial concentration) was carried out in two independent laboratories with the same photocatalytic device and with various analytical procedures. Comparison of the degradation rate and of the mineralization efficiency allowed the determination of the clean air delivery rate in both cases. Formaldehyde was the only by-product detected during photocatalytic test under standardized experimental conditions. The concentration of transient formaldehyde varied according to the initial VOC concentration. Moreover the photocatalytic reaction rate of formaldehyde in mixture with other pollutants was analysed. It was concluded that formaldehyde concentration did not increase with time.

Conclusion??perspective

This type of experiment should allow the comparison of the performances of different photoreactors and of photocatalytic media under controlled and reproducible conditions against mixtures of pollutants including formaldehyde.  相似文献   

9.

Background

The photocatalytic degradation of pyrene under UV (125?W Hg-Arc, 10.4?mW/cm2) irradiation of TiO2 aqueous suspension has been found to be highly improved with the dissolved transition metal ions like Cu2+, Fe3+, Ag+, and Au3+, etc. As the reduction potential of these metals lies below the conduction band (CB) position (?0.1?eV) of TiO2, the photoexcited electron transfer occurs more readily and reduces electron?Chole recombination rate. Therefore, it has a beneficial influence on the photocatalytic ability of TiO2 because of rapid Fermi energy equilibrium between the CB of TiO2 and its surface adsorbed metal ions.

Results and discussion

The Fermi level is referred to as the electrochemical potential and plays an important role in the band theory of solids. When metal and semiconductor are in contact, electron migration from photoirradiated semiconductor to the deposited metal occurs at the interface until two Fermi levels equilibrate and enhanced the photocatalytic activity of semiconductor photocatalyst. Ni2+ having more negative reduction potential (?0.25?eV) than the CB of TiO2 imparts negligible co-catalytic activity to TiO2 photoreaction. It also revealed that loading of Au3+ ions displayed higher degradation rate of pyrene than Au photodeposition. Furthermore, when the amount of dissolved Fe+3 and Au3+ ions gradually increases from 0.1 to 2?wt.%, the pyrene photodecomposition rate also become faster.  相似文献   

10.

Introduction

This study of photocatalytic degradation of wastewater was carried out in alveolar cell ??-SiC foam-structured photocatalytic reactors working in a recirculation mode. The immobilization of TiO2 on ??-SiC foams was efficiently obtained through a sol?Cgel technique in acidic conditions.

Discussion

In order to optimize degradation yields obtained by the foam-structured prototype reactor for the photocatalytic water treatment, the operating conditions of the photoreactor have been investigated and the efficiency of the process was evaluated by measuring the photocatalytic degradation of Diuron (3-(3,4-dichlorophenyl)-1,1-dimethyl-urea)) under UV irradiation. Kinetic studies were carried out by investigating the influence of different parameters controlling the reaction (TiO2 loading and ??-SiC foam cell size). The ageing of TiO2/??-SiC foam photocatalytic materials and the mineralization (TOC, Cl?, NO3? and NH4+) of Diuron were investigated.  相似文献   

11.

Introduction

In this work, we report in situ studies of UV photoelectrocatalytic discoloration of a dye (indigo carmine) by a TiO2 thin film in a microreactor to demonstrate the driving force of the applied electrode potential and the dye flow rate toward dye discoloration kinetics.

Methods

TiO2 65-nm-thick thin films were deposited by PVD magnetron sputtering technique on a conducting glass substrate of fluorinated tin oxide. A microreactor to measure the discoloration rate, the electrode potential, and the photocurrent in situ, was developed. The dye solutions, before and after measurements in the microreactor, were analyzed by Raman spectroscopy.

Results

The annealed TiO2 thin films had anatase structure with preferential orientation (101). The discoloration rate of the dye increased with the applied potential to TiO2 electrode. Further, acceleration of the photocatalytic reaction was achieved by utilizing dye flow recirculation to the microreactor. In both cases the photoelectrochemical/photocatalytic discoloration kinetics of the dye follows the Langmuir?CHinshelwood model, with first-order kinetics.

Conclusions

The feasibility of dye discoloration on TiO2 thin film electrodes, prepared by magnetron sputtering using a flow microreactor system, has been clearly demonstrated. The discoloration rate is enhanced by applying a positive potential (E AP) and/or increasing the flow rate. The fastest discoloration and shortest irradiation time (50?min) produced 80% discoloration with an external anodic potential of 0.931?V and a flow rate of 12.2?mL?min?1.  相似文献   

12.

Introduction

TiO2 anatase nanoplates and hollow microspheres were fabricated by a solvothermal?Chydrothermal method using titanium isopropoxide as a titanium precursor and hydrofluoric acid as a capping agent in order to enhance the formation of the {001} crystal facets of the anatase nanocrystals.

Methods

These different morphological structures of TiO2 anatase can be achieved by only changing the solvent, keeping the amount of the precursor and of the capping agent identical during the solvothermal?Chydrothermal process.

Results and discussion

After calcination of the samples, the adsorbed fluoride atoms on the {001} crystal facets of the TiO2 anatase nanocrystals were completely removed from their surface according to XPS analysis. The calcined TiO2 anatase structures were higher crystallized and the specific surface area of the catalysts increased, enhancing their photocatalytic activity in comparison to the non-calcined TiO2 anatase structures. All TiO2 anatase samples with adsorbed as well as non-adsorbed fluoride atoms on their {001} crystal facets, exhibited a higher photonic efficiency than Degussa P25, which was used as a reference.

Conclusion

The fluoride free TiO2 anatase nanoplates exhibited the best photocatalytic activity in oxidizing the NO gas to NO2 and NO3 ?.  相似文献   

13.

Background and purpose

The biosorption of Cr(VI) from aqueous solution has been studied using free and immobilized Pediastrum boryanum cells in a batch system. The algal cells were immobilized in alginate and alginate?Cgelatin beads via entrapment, and their algal cell free counterparts were used as control systems during biosorption studies of Cr(VI).

Methods

The changes in the functional groups of the biosorbents formulations were confirmed by Fourier transform infrared spectra. The effect of pH, equilibrium time, initial concentration of metal ions, and temperature on the biosorption of Cr(VI) ion was investigated.

Results

The maximum Cr(VI) biosorption capacities were found to be 17.3, 6.73, 14.0, 23.8, and 29.6?mg/g for the free algal cells, and alginate, alginate?Cgelatin, alginate?Ccells, and alginate?Cgelatin?Ccells at pH?2.0, which are corresponding to an initial Cr(VI) concentration of 400?mg/L. The biosorption of Cr(VI) on all the tested biosorbents (P. boryanum cells, alginate, alginate?Cgelatin, and alginate?Ccells, alginate?Cgelatin?Ccells) followed Langmuir adsorption isotherm model.

Conclusion

The thermodynamic studies indicated that the biosorption process was spontaneous and endothermic in nature under studied conditions. For all the tested biosorbents, biosorption kinetic was best described by the pseudo-second-order model.  相似文献   

14.

Purpose

Biodegradation and biodecolorization of Drimarene blue K2RL (anthraquinone) dye by a fungal isolate Aspergillus flavus SA2 was studied in lab-scale immobilized fluidized bed bioreactor (FBR) system.

Method

Fungus was immobilized on 0.2-mm sand particles. The reactor operation was carried out at room temperature and pH?5.0 in continuous flow mode with increasing concentrations (50, 100, 150, 200, 300, 500?mg?l?1) of dye in simulated textile effluent on the 1st, 2nd, 5th, 8th, 11th, and 14th days. The reactors were run on fill, react, settle, and draw mode, with hydraulic retention time (HRT) of 24?C72?h. Total run time for reactor operation was 17?days.

Results

The average overall biological oxygen demand (BOD), chemical oxygen demand (COD), and color removal in the FBR system were up to 85.57%, 84.70%, and 71.3%, respectively, with 50-mg?l?1 initial dye concentration and HRT of 24?h. Reductions in BOD and COD levels along with color removal proved that the mechanism of biodecolorization and biodegradation occurred simultaneously. HPLC and LC?CMS analysis identified phthalic acid, benzoic acid, 1, 4-dihydroxyanthraquinone, 2,3-dihydro-9,10-dihydroxy-1,4-anthracenedione, and catechol as degradation products of Drimarene blue K2RL dye. Phytotoxicity analysis of bioreactor treatments provided evidence for the production of less toxic metabolites in comparison to the parent dye.

Conclusion

The present fluidized bed bioreactor setup with indigenously isolated fungal strain in its immobilized form is efficiently able to convert the parent toxic dye into less toxic by-products.  相似文献   

15.

Introduction

Two semi-specific microbial biosensors were constructed for the analysis of biochemical oxygen demand (BOD) in high-cellulose-content pulp and paper industry wastewaters. The biosensors were based on living cells of Bacillus subtilis and Paenibacillus sp. immobilized in an agarose gel matrix. Semi-specific microorganisms were isolated from various samples (decaying sawdust and rabbit manure) and were chosen based on their ability to assimilate cellulose.

Materials &; methods

The biosensors were calibrated with the Organization for Economic Cooperation and Development synthetic wastewater, and measurements with different wastewaters were conducted.

Results

The response time of biosensors using the steady-state method was 20?C25 min, and the service life of immobilized microorganisms was 96 days. Detection limit was 5 mg/l of BOD7 while linear ranges extended up to 55 and 50 mg/l of the BOD7 for B. subtilis- and Paenibacillus sp.-based biosensors, respectively. Repeatability and reproducibility of both biosensors were within the limits set by APHA??less than 15.4%. In comparison, both biosensors overestimated the BOD7 values in paper mill wastewaters and underestimated the BOD7 in aspen pulp mill wastewater.

Conclusions

The semi-specific biosensors are suitable for the estimation of organic pollution derived from cellulose, while the detection of pollution derived from tannins and lignins was minor. Better results in terms of accuracy and repeatability were gained with Paenibacillus sp. biosensor.  相似文献   

16.

Introduction

Schwertmannite was synthesized through an oxidation of FeSO4 by Acidithiobacillus ferrooxidans LX5 cell suspension at an initial pH?2.5 and 28°C for 3?days and characterized using X-ray diffraction spectroscopy and scanning electron microscope. The schwertmannite photocatalytic degradation of methyl orange (MO) by oxalate was investigated at different initial pH values, concentrations of schwertmannite, oxalate, and MO.

Results

The results demonstrated that photodegradation of MO in the presence of schwertmannite or oxalate alone was very weak. However, the removal of MO was significantly enhanced when schwertmannite and oxalate coexisted in the reaction system. Low pH (4 or less) was beneficial to the degradation of MO. The optimal doses of schwertmannite and oxalate were 0.2?g?L?1 and 2?mM, respectively. Hydroxyl radicals (·OH) and Fe(II), the intermediate products, were also examined during the reaction to explore their correlation with the degradation of MO.

Conclusion

A possible mechanism for the photocatalytic decomposition of MO in the study was proposed. The formation of Fe(III)-oxalate complexes on the surface of schwertmannite was a precursor of H2O2 and Fe(II) production, further leading to the yield of ·OH responsible for the decomposition of MO.  相似文献   

17.

Introduction

The copper bioaccumulation by the floating Lemna minor and by the completely submerged Ranunculus tricophyllus as a function of exposure time and copper concentration was studied, with the aim of proposing these species as environmental biosensors of the water pollution.

Results

The results show that both these aquatic angiosperms are good indicators of copper pollution because the copper uptake is the only function of metal concentration (water pollution).

Conclusion

Uptake behavior is reported as a function of the time and concentration, based on the results of a 3-year study. Kinetic evaluations are proposed.  相似文献   

18.
Zhang M  An T  Fu J  Sheng G  Wang X  Hu X  Ding X 《Chemosphere》2006,64(3):423-431
An adsorptive silica-supported titania photocatalyst TiO(2)/SiO(2) was prepared by using nanosized titania (anatase) immobilized on silica gel by the sol-gel technique with the titanium tetra isopropoxide as the main raw material and acetic acid as the acid catalyst. Meanwhile the structure and properties of the TiO(2)/SiO(2) photocatalyst were studied by means of many modern analysis techniques such as TEM, XRD, and BET. Gas-solid heterogeneous photocatalytic decomposition of four carbonyl compounds mixture at low concentration levels over ultraviolet irradiated TiO(2)/SiO(2) photocatalyst were carried out with high degradation efficiencies in a coaxial triple-cylinder-type fluidized bed photocatalytic reactor, which provided efficient continuous contact of ultraviolet photons, silica-supported titania photocatalyst, and gaseous reactants. Experimental results showed that the photocatalyst had a high adsorption performance and a good photocatalytic activity for four carbonyl compounds mixture. Some factors influencing the photocatalytic decomposition of the mixed carbonyl compounds, i.e. the gas flowrate, relative humidity, concentration of oxygen, and illumination time, were discussed in detail. It is found that the photocatalytic reaction rate of four carbonyl compounds decreased in this order: propionaldehyde, acetone, acetaldehyde and formaldehyde.  相似文献   

19.

Introduction

The changes in photosynthetic pigments, chlorophyll fluorescence, protein content, and antioxidant enzymes were investigated in a foliose lichen Pyxine cocoes, which was subjected to increasing concentrations of arsenate.

Methods

The arsenate concentrations of 10, 25, 50, 75, 100, and 200???M were sprayed every alternate day on the lichen thallus. The thalli were then harvested on 10, 20, 30, and 45?days.

Results

The quantity of photosynthetic pigments exhibited a decreasing trend till 20?days but increased from 30?days onwards. Concomitantly, chlorophyll fluorescence also showed a decreasing trend with increasing arsenic treatment duration as well as concentration. The higher concentration of arsenate was found to be deleterious to the photosynthesis of lichen as the chlorophyll fluorescence and the amount of pigments decreased significantly. The protein content of lichen increased uninterruptedly as the concentration of arsenate as well as duration of treatment increased. The activities of superoxide dismutase and ascorbate peroxide increased initially at lower concentration of arsenate but declined at higher concentrations and longer duration of treatment.

Conclusions

The catalase activity was found to be most susceptible to arsenate stress as its activity started declining from very beginning of the experiment. P. cocoes also proved to be an excellent accumulator of arsenate whose concentration increased in the thallus corresponding to its increase in the treatment and duration. Thus, it can be utilized for active biomonitoring of arsenic pollution.  相似文献   

20.

Purpose

The aim of this study is to develop a normalization method for real-time PCR data by analyzing the most stably expressed control genes in mussel (Mytilus edulis) reproductive tissue.

Methods

To facilitate this, six candidate genes, including several commonly used in the literature, were investigated in mussels at different stages of gametogenesis and following experimental exposure to a model estrogen (17b-estradiol). GeNorm and NormFinder softwares were employed to assess the stability of the reference genes.

Results

Our results demonstrate that the most stable reference genes are not the same in mussels at different stages of gametogenesis and in experimentally E2-exposed mussels. Interestingly, HEL (helicase) and ACT (actin) mRNA expression levels were most affected by the stage of gametogenesis and yet, in molluscan studies, ACT is possibly the most frequently used reference gene.

Conclusions

We demonstrate that the experimental results are highly dependent on the reference gene chosen and that statistically significant contrasting differences between sample groups are present or absent depending on the reference gene employed.  相似文献   

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