Effect of operational parameters on photodegradation of methylene blue on ZnS nanoparticles prepared in presence of an ionic liquid as a highly efficient photocatalyst

In the present study, photocatalytic degradation of methylene blue (MB) on ZnS nanoparticles, prepared in aqueous solution of a room-temperature ionic liquid (RTIL), was studied and the results were compared with commercial ZnS. Influence of various operational parameters such as calcination temperature, catalyst weight, pH of solution, and initial concentration of MB on the photodegradation reaction was investigated to achieve maximum degradation efficiency. The optimum value of pH and catalyst dose was found to be 9.5 and 0.6 g l^-1. It was demonstrated that the photodegradation of MB follows a pseudo first-order kinetic. At optimized conditions, the rate constant of the reaction on ZnS nanoparticles prepared in aqueous solution of the RTIL is about five and four times greater than the prepared sample in water and commercial ZnS, respectively.     

Photocatalytic degradation of methylene blue and phenol on Fe-doped sulfated titania

Fe-doped sulfated titania (FST) photocatalysts with high photocatalytic activity were prepared from industrial titanyl sulfate solution and characterized using X-ray diffraction (XRD), thermogravimetry analysis?Cdifferential scanning calorimeter (TGA-DSC), Fourier transform infrared spectroscopy (FT-IR), and nitrogen adsorption?Cdesorption techniques. The photocatalytic activity of the FST photocatalyst was evaluated using the photodegradation of methylene blue (MB) and the photooxidation of phenol in aqueous solutions in the presence of UV irradiation, respectively. The effect of various parameters, such as calcining temperature, calcination time, initial concentration of substrate, amount of catalyst and pH value on the photocatalytic activity of FST photocatalyst was investigated. Among the parameters studied, calcining temperature, initial concentration of substrate, and amount of catalyst have a very similar effect on the activity of FST photocatalyst for both the photodegradation of MB and the photooxidation of phenol, while the others have distinct differences. The optimal calcination conditions were 500?°C, 1.5?h and 650?°C, 2.5?h; the optimal catalyst concentration were 1.0 and 1.2?g?L^?1; the optimal pH values were 8 and 4 for the photodegradation of MB and the photooxidation of phenol, respectively. In addition, the mechanism for the high photocatalytic efficiency of FST photocatalyst has also been put forward.     

Fe3O4@SiO2@TiO2-Co/rGO磁性光催化剂的合成及其光催化活性研究

采用溶胶-凝胶法和水热法（HTM）合成了Fe₃O₄@SiO₂@TiO₂-Co/rGO复合纳米粒子（磁性光催化剂）,通过X射线衍射、扫描电子显微镜及其能量分散光谱和UV-vis漫反射光谱对产物进行了表征分析.研究了Co掺杂量、溶液pH值、亚甲基蓝（MB）溶液初始浓度以及干扰离子（例如Cl^-、SO₄^2-、CO₃^2-）等因素对MB降解的影响,并对磁性光催化剂的可重复使用性进行了分析.正常实验条件下（pH=7,[MB]=10 mg/L,磁性光催化剂用量=0.1 g/50 mL）,150 min内MB最大去除率达到98.24%.干扰离子影响MB降解次序为CO₃^2- < Cl^- < SO₄^2-,磁性光催化剂重复使用7次MB光降解率仅下降7.07%,新型磁性光催化剂具有良好的MB降解性能和较高的重复使用性能.     

Ultrasound‐assisted Synthesis of Ag‐ZnS/rGO and its Utilization in Photocatalytic Degradation of Tetracycline Under Visible Light Irradiation

Recent improvements based on heterojunction nanocomposites have opened new possibilities in photocatalysis. In this research, an ultrasound‐assisted coprecipitation method was used to fabricate silver, zinc sulfide and reduced graphene oxide (Ag‐ZnS/rGO) nanocomposite, and characterization results indicated that 3% Ag‐ZnS spherical nanoparticles are successfully embedded in rGO matrix. The potential of the Ag‐ZnS/rGO, as a visible light active photocatalyst, was assessed through optimizing degradation of Tetracycline (TC) by response surface methodology. It was found that the photocatalytic degradation of TC increased with an increase in the amount of nanocomposite and irradiation time, whereas it decreased with increasing the initial TC concentration. Under the optimal conditions (10 mg L^?1 of TC, 1.25 g L^?1 of Ag‐ZnS/rGO, at pH = 7, and irradiation duration 110 min), more than 90% of the TC was degraded. The study of the mechanism of the photocatalytic process disclosed that the synergistic role of surface plasmon resonance (SPR) induced by Ag nanoparticles and p‐type semiconductor feature of rGO leads to ZnS semiconductor stimulation in the visible light region. Eventually, a pseudo‐first order kinetics model was developed based on the proposed mechanism. The obtained results highlight the role of Ag‐ZnS/rGO nanophotocatalyst toward degradation of some antibiotics under visible light.     

ZnS微米花的水热合成及光催化性质研究

本文采用简便的水热法一步合成ZnS微米花,通过X射线衍射仪、扫描电子显微镜等表征手段研究了合成产物的形貌及微观结构,并考察了合成产物的光催化性质。合成产物的光催化测试结果表明,在紫外光辐照下,产物对亚甲基蓝、甲基橙和曙红都有很好的降解效果。为了测试产物循环利用的光催化能力,对其进行了5次降解实验,结果显示产物依然保持良好的光催化活性。     

ZnS quantum dots derived a reagentless uric acid biosensor

A reagentless amperometric uric acid biosensor based on zinc sulfide (ZnS) quantum dots (QDs) was firstly developed. It could detect uric acid without the presence of an electron mediator. The carboxyl group functionalized ZnS QDs were synthesized, and they were soluble biocompatible and conductive. ZnS QDs conjugates could provide increased enzyme binding sites, which may result in higher enzyme loading. Thus, the proposed uricase/ZnS QDs/l-cys biosensor exhibited higher amperometric response compared to the one without QDs (uricase/l-cys biosensor). In addition, there was little AA interference. It showed a linear dependence on the uric acid concentration ranging from 5.0 × 10⁻⁶ to 2.0 × 10⁻³ mol L⁻¹ with a detection limit of 2.0 × 10⁻⁶ mol L⁻¹ at 3σ.     

The Role of the Relative Dye/Photocatalyst Concentration in TiO2 Assisted Photodegradation Process

Despite photocatalytic degradation is studied generally focusing the catalyst, its interaction with the contaminant molecule plays a fundamental role in the efficiency of that process. Then, we proposed a comparative study about the photodegradation of two well‐known dyes, with different acidity/basicity – Methylene Blue (MB) and Rhodamine B (RhB), catalyzed by TiO₂ nanoparticles, varying both dye and photocatalyst concentrations. The results showed that the amphoteric character of MB molecules, even in a range of concentration of 5.0–10.0 mg L^?1, did not imply in pH variation in solution. Therefore, it did not affect the colloidal behavior of TiO₂ nanoparticles, independent of the relative dye/catalyst concentration. The acid–base character of RhB influenced the resultant pH of the solution, implicating in different colloidal behavior of the nanoparticles and consequently, in different degradation conditions according to dye concentration. As the isoelectric point of TiO₂ is between the pH range of the RhB solutions used in this study, from 1.0 to 7.5 mg L^?1, the resultant pH was the key factor for degradation conditions, from a well dispersed to an agglomerated suspension.     

ZnS光催化剂对不同偶氮类染料光降解的光催化性能的比较

在表面活性剂十六烷基三甲基溴化铵(CTAB)存在时,合成了ZnS光催化剂。 采用X射线衍射和透射电子显微镜等测试技术结果表明,制得的ZnS粒子尺寸均一,无团聚现象,平均粒径约为3.5 nm。 研究了ZnS光催化剂在紫外光下对不同染料的光催化降解效率,结果表明,ZnS光催化剂对一些含-N=N-基团的偶氮类染料,如甲基橙(MO)、酸性嫩黄(AY)、酸性橙Ⅱ(AOⅡ)光催化降解效率高达88％以上,甲基红(MR)的光催化降解效率也达59.63%。 表明-N=N-基团容易降解。 染料分子本身的吸光性也起一定的作用,虽然二甲酚橙(XO)和亚甲基蓝(MB)分子中均不含-N=N-基团,但由于XO的最大吸收峰分布于430 nm的紫外光区,其光催化降解效率可达43.83％,而MB最大吸收峰分布于664 nm可见光区,因此,其光催化降解效率则非常低。     

Selective and specific detection of sulfate-reducing bacteria using potentiometric stripping analysis

A fast, sensitive and reliable potentiometric stripping analysis (PSA) is described for the selective detection of the marine pathogenic sulfate-reducing bacterium (SRB), Desulforibrio caledoiensis. The chemical and electrochemical parameters that exert influence on the deposition and stripping of lead ion, such as deposition potential, deposition time and pH value were carefully studied. The concentration of SRB was determined in acetate buffer solution (pH 5.2) under the optimized condition (deposition potential of −1.3 V, deposition time of 250 s, ionic strength of 0.2 mol L⁻¹ and oxidant mercury (II) concentration of 40 mg L⁻¹). A linear relationship between the stripping response and the logarithm of the bacterial concentration was observed in the range of 2.3 × 10 to 2.3 × 10⁷ cfu mL⁻¹. In addition, the potentiometric stripping technique gave a distinct response to the SRB, but had no obvious response to Escherichia coli. The measurement system has a potential for further applications and provides a facile and sample method for detection of pathogenic bacteria.     

Novel ZnS/Carbon Nanofiber Photocatalyst for Degradation of Rhodamine 6G: Kinetics Tracking of Operational Parameters and Development of a Kinetics Model

A novel nanocomposite in the role of photocatalyst was prepared by composition of zinc sulfide (ZnS) nanoparticles with carbon nanofibers (CNFs) and was characterized. The XRD, EDX, and FE‐SEM analysis revealed that ZnS is successfully embedded in CNFs matrix. The DRS results indicated that supporting of ZnS by CNFs led to a decrease of the band gap energy. The photocatalytic degradation of a hazardous xanthine dye, Rhodamine 6 G (Rh‐6G), by the prepared ZnS/CNFs composite was examined from the kinetics point of view. Nonlinear regression analysis was used to develop a mathematical kinetics model based on the Langmuir–Hinshelwood mechanism, and an empirical equation was obtained for the estimation of apparent pseudo‐first‐order rate constant (k_ap) as a function of operational parameters (viz. initial dye concentration, ZnS/CNFs content, pH, and irradiation intensity). Based on the results, k_ap increased with an increase ZnS/CNFs content, pH, and UV light intensity, whereas it decreased by increasing the initial Rh‐6G concentration. Moreover, a new kinetics model was obtained based on proposed elementary steps to determine k_ap. In the final stage of the work, intermediate materials produced within photocatalytic degradation of Rh‐6G dye were detected by GC‐MS analysis.     

Synthesis,characterization and photocatalytic application of TiO2/magnetic graphene for efficient photodegradation of crystal violet

A magnetized nano‐photocatalyst based on TiO₂/magnetic graphene was developed for efficient photodegradation of crystal violet (CV). Scanning electron microscopy, X‐ray diffraction, energy‐dispersive X‐ray spectroscopy and elemental mapping were used to characterize the prepared magnetic nano‐photocatalyst. The photocatalytic activity of the synthesized magnetic nano‐photocatalyst was evaluated using the decomposition of CV as a model organic pollutant under UV light irradiation. The obtained results showed that TiO₂/magnetic graphene exhibited much higher photocatalytic performance than bare TiO₂. Incorporation of graphene enhanced the activity of the prepared magnetic nano‐photocatalyst. TiO₂/magnetic graphene can be easily separated from an aqueous solution by applying an external magnetic field. Effects of pH, magnetized nano‐photocatalyst dosage, UV light irradiation time, H₂O₂ amount and initial concentration of dye on the photodegradation efficiency were evaluated and optimized. Efficient photodegradation (>98%) of the selected dye under optimized conditions using the synthesized nano‐photocatalyst under UV light irradiation was achieved in 25 min. The prepared magnetic nano‐photocatalyst can be used in a wide pH range (4–10) for degradation of CV. The effects of scavengers, namely methanol (OH^? scavenger), p‐benzoquinone (O₂^?? scavenger) and disodium ethylenediaminetetraacetate (hole scavenger), on CV photodegradation were investigated.     

Enhanced photocatalytic activity,mechanism and potential application of Idoped-Bi4Ti3O12 photocatalysts

In this study, we have introduced iodine into Bi₄Ti₃O₁₂ (BTO) crystals with the aim of improving their photocatalytic activities in decomposing organic pollutants. The as-prepared I_doped-BTO photocatalysts were systematically analyzed by various techniques (e.g. X-ray powder diffraction, scanning electron microscopy, transmission electron microscopy, X-ray photoelectron spectroscopy, ultraviolet–visible diffuse reflectance spectroscopy and Fourier transform infrared spectroscopy), as well as density functional theory calculation. It is confirmed that I element is successfully doped, as an I^? oxidation state, in the BTO crystals by substituting the O in the perovskite-like (Bi₂Ti₃O₁₀)^2? blocks. The photocatalytic activities between the I_x-BTO (x = 0, 0.2, 0.4, 0.6, and 0.8) samples were compared by the photodegradation of methylene blue (MB) under simulated-sunlight irradiation, revealing that I_0.4-BTO is the optimal photocatalyst having a photocatalytic activity about 3.0 times higher than that of parent BTO. Based on the experimental data and density functional theory calculation, the enhanced photocatalytic mechanism for the I_doped-BTO photocatalysts was proposed and discussed. To promote the potential application of the optimal I_0.4-BTO photocatalyst, its photocatalytic performances were further investigated by the photodegradation of ciprofloxacin, tetrabromobisphenol A, tetracycline hydrochloride and methyl orange/rhodamine B (RhB)/MB mixture dyes; moreover, the effect of inorganic anions and pH values on the MB photodegradation was also investigated.     

AgBr/nanoAlMCM-41 visible light photocatalyst for degradation of methylene blue dye

A novel photocatalytic material was synthesized by dispersion of AgBr in nanoAlMCM-41 material. The AgBr/nanoAlMCM-41 sample shows strong absorption in the visible region because of the plasmon resonance of Ag nanoparticles in AgBr/nanoAlMCM-41. The catalysts were characterized using XRD (X-ray diffraction), UV-visible diffused reflectance spectra (UV-vis DRS) and scanning electron microscopy (SEM). The photocatalytic activity and stability of the synthesized catalysts were evaluated for methylene blue (MB) degradation in aqueous solution in the presence of 200 W tungsten filament Philips lamp. Several parameters were examined, catalyst amount, pH and initial concentration of MB, AgBr loading. The effect of dosage of photocatalyst was studied in the range 0.05-1.00 g/L. It was seen that 0.1 g/L of photocatalyst is an optimum value for the dosage of photocatalyst. The support size was obtained about 9-100 nm. In the same way, the average size of AgBr nanoparticles was about 10nm before visible radiation. After visible radiation the average size of AgBr nanoparticles was about 25 nm.     

Colorimetric detection of iron ions (III) based on the highly sensitive plasmonic response of the N-acetyl-l-cysteine-stabilized silver nanoparticles

We report here a facile colorimetric sensor based on the N-acetyl-l-cysteine (NALC)-stabilized Ag nanoparticles (NALC–Ag NPs) for detection of Fe³⁺ ions in aqueous solution. The Ag NPs with an average diameter of 6.55 ± 1.0 nm are successfully synthesized through a simple method using sodium borohydride as reducing agent and N-acetyl-l-cysteine as protecting ligand. The synthesized silver nanoparticles show a strong surface plasmon resonance (SPR) around 400 nm and the SPR intensity decreases with the increasing of Fe³⁺ concentration in aqueous solution. Based on the linear relationship between SPR intensity and concentration of Fe³⁺ ions, the as-synthesized water-soluble silver nanoparticles can be used for the sensitive and selective detection of Fe³⁺ ions in water with a linear range from 80 nM to 80 μM and a detection limit of 80 nM. On the basis of the experimental results, a new detection mechanism of oxidation–reduction reaction between Ag NPs and Fe³⁺ ions is proposed, which is different from previously reported mechanisms. Moreover, the NALC–Ag NPs could be applied to the detection of Fe³⁺ ions in real environmental water samples.     

花状ZnO/ZnS异质结构的简易合成、结构表征及光催化活性

采用简便的两步溶液相化学方法,在较低温度下(80℃),制备出了花状的ZnO/ZnS异质结构。分别利用X射线衍射、X射线光电子能谱仪、扫描电子显微镜、透射电子显微镜、紫外-可见光谱仪等测试手段对所制备的样品进行表征,结果表明ZnO/ZnS异质结构是由花状ZnO纳米结构和ZnS纳米粒子组成。在光降解罗丹明B(RhB)的测试中,ZnO/ZnS异质结构样品体现出了比ZnO前驱物和商业P25光催化剂更高的光催化效率,这主要可归因于异质结构更有利于电子-空穴的有效分离。ZnO/ZnS光催化剂体现出良好的循环稳定性。     

Ag@AgBr光催化剂的制备及其可见光催化降解亚甲基蓝反应性能

采用沉积-沉淀及光还原法制备了Ag@AgBr等离子体光催化剂,利用X射线衍射、扫描电镜和紫外-可见漫反射光谱对其进行了表征,并考察了该等离子体光催化剂在可见光(λ420nm)下的催化性能,探讨了催化剂用量、pH值、亚甲基蓝初始浓度、H2O2添加量、循环使用及捕获剂对Ag@AgBr催化性能的影响.结果表明,当亚甲基蓝的初始浓度为10mg/L,催化剂用量为1g/L,pH=9.8时,光照12min后,亚甲基蓝的降解率高达96%,且样品经5次循环使用后活性基本保持不变;而少量H2O2的添加对光催化活性影响不大,过量的H2O2会降低光催化活性;乙二胺四乙酸捕获空穴后比异丙醇捕获·OH后的光催化活性降得更低.同时,对Ag@AgBr等离子体光催化剂可见光降解亚甲基蓝的催化机理进行了分析.     

Highly sensitive hydrazine chemical sensor based on mono-dispersed rapidly synthesized PEG-coated ZnS nanoparticles

Monodispersed PEG-coated ZnS (P-ZnS) nanoparticles (NPs) were synthesized by facile microwave process and utilized as efficient electron mediators for the fabrication of highly sensitive hydrazine chemical sensor. The detailed morphological and structural properties revealed the monodispersity and good crystallinity for synthesized P-ZnS NPs. A high-sensitivity of ∼89.3 μA cm⁻² μM and low limit of detection of 1.07 μM, based on S/N ratio, were obtained for the fabrication of hydrazine chemical sensor based on P-ZnS NPs. To the best of our knowledge, this is the first report which demonstrates the utilization of P-ZnS NPs for the fabrication of efficient hydrazine chemical sensor. By this work, it could be concluded that simply synthesized ZnS NPs can be used as efficient electron mediators for the fabrication of effective hydrazine chemical sensors.     

Highly-controllable imprinted polymer nanoshell at the surface of silica nanoparticles based room-temperature phosphorescence probe for detection of 2,4-dichlorophenol

This paper reports a facile and general method for preparing an imprinted polymer thin shell with Mn-doped ZnS quantum dots (QDs) at the surface of silica nanoparticles by stepwise precipitation polymerization to form the highly-controllable core–shell nanoparticles (MIPs@SiO₂–ZnS:Mn QDs) and sensitively recognize the target 2,4-dichlorophenol (2,4-DCP). Acrylamide (AM) and ethyl glycol dimethacrylate (EGDMA) were used as the functional monomer and the cross-linker, respectively. The MIPs@SiO₂–ZnS:Mn QDs had a controllable shell thickness and a high density of effective recognition sites, and the thickness of uniform core–shell 2,4-DCP-imprinted nanoparticles was controlled by the total amounts of monomers. The MIPs@SiO₂–ZnS:Mn QDs with a shell thickness of 45 nm exhibited the largest quenching efficiency to 2,4-DCP by using the spectrofluorometer. After the experimental conditions were optimized, a linear relationship was obtained covering the linear range of 1.0–84 μmol L⁻¹ with a correlation coefficient of 0.9981 and the detection limit (3σ/k) was 0.15 μmol L⁻¹. The feasibility of the developed method was successfully evaluated through the determination of 2,4-DCP in real samples. This study provides a general strategy to fabricate highly-controllable core–shell imprinted polymer-contained QDs with highly selective recognition ability.     

Facile synthesis of N-acetyl-L-cysteine capped ZnS quantum dots as an eco-friendly fluorescence sensor for Hg2+

This paper described an investigation of a novel eco-friendly fluorescence sensor for Hg²⁺ ions based on N-acetyl-l-cysteine (NAC)-capped ZnS quantum dots (QDs) in aqueous solution. By using safe and low-cost materials, ZnS QDs modified by NAC were easily synthesized in aqueous medium via a one-step method. The quantitative detection of Hg²⁺ ions was developed based on fluorescence quenching of ZnS QDs with high sensitivity and selectivity. Under optimal conditions, its response was linearly proportional to the concentration of Hg²⁺ ions in a range from 0 to 2.4 × 10⁻⁶ mol L⁻¹ with a detection limit of 5.0 × 10⁻⁹ mol L⁻¹. Most of common physiologically relevant cations and anions did not interfere with the detection of Hg²⁺. The proposed method was applied to the trace determination of Hg²⁺ ions in water samples. The possible quenching mechanism was also examined by fluorescence and UV-vis absorption spectra.     

Green synthesis of activated carbon doped tungsten trioxide photocatalysts using leaf of basil (Ocimum basilicum) for photocatalytic degradation of methylene blue under sunlight

Tungsten oxide (WO₃) nanoparticles were prepared hydrothermally by basil leaves extract, and Activated Carbon (AC) was prepared by the carbonization of date pits. Moreover, 1, 2 and 3% of AC doped WO₃ nanoparticles have been fabricated under hydrothermal conditions. The obtained samples have been characterized by using different techniques such as x-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), simultaneous thermogravimetric analysis (TG-DTGA), fourier transform infrared (FT-IR), BET surface area, and Ultra-Violet spectroscopy (UV–Vis). It was observed that band-gap energy of the fabricated materials decreases by increasing AC amount. Similarly, BET surface area and porosity results showed increasing the content of AC, surface area, pore size and pore volume were decreased. The functional groups, determined by FT-IR, played a significant role in the photocatalytic performance. The photocatalytic performance of fabricated samples was used for the degradation of methylene blue (MB) at neutral pH under visible light radiations, and it is observed that WO₃/3%AC photocatalyst showed the highest degradation of MB. Both, capped phytochemicals of basil extract and the nanocomposites, were improved the photocatalytic performance, about 94% photodegradation was observed within 25 min under the reaction conditions. The photocatalyst was stable and about 85% and 81% photodegradation of MB were found under the two times of reusability tests.