Well-designed ZnIn2S4/TiO2 Z-type heterojunction for efficient photocatalytic reduction of Cr(VI)

ZnIn₂S₄/TiO₂ photocatalyst was obtained by a facile hydrothermal method. Various techniques were used to characterize the ZnIn₂S₄/TiO₂, crystal structure and optical properties of ZnIn₂S₄/TiO₂. Cr (Ⅵ) as highly-toxic pollutant was used as the target reduction product to evaluate the catalytic performance of ZnIn₂S₄/TiO₂ under visible light irradiation. According to the experiment results, the reduction rate of Cr(VI) in the presence of ZnIn₂S₄/TiO₂ reaches 99% within 60 min, which is much better than ZnIn₂S₄ and TiO₂, respectively. At the same time, ZnIn₂S₄/TiO₂ also performs good stability for reduction rate hardly changes after 5 recycling experiments.     

Cr(VI)-乙酸复合体系中硫酸盐掺杂的含钛高炉渣光催化还原Cr(VI)

采用煅烧的硫酸盐掺杂的含钛高炉渣作光催化剂,研究了Cr(VI)-乙酸(AA)复合体系中Cr(VI)的光催化还原效率,考察了初始pH值、Cr(VI)初始浓度、AA/Cr(VI)体积比、协同效率因子、光催化剂使用寿命等因素的影响. 结果表明,增大AA/Cr(VI)比到0.2%,Cr(VI)的还原效率先增大到27.55%随后逐渐降低. 酸性条件下,Cr(VI)单一体系和Cr(VI)-AA复合体系中Cr(VI)的还原率和吸附率都明显提高;相同反应时间下(110 min),初始pH 1.5时,2种体系中Cr(VI)的还原效率分别为76.32%(单一体系)和100%(复合体系). 复合体系中协同效率因子始终大于0. 循环使用5次后催化剂对Cr(VI)的光催化还原率为92.2%. Cr(VI)在Cr(VI)-AA体系中的光催化还原遵循Langmuir-Hinshelwood动力学规律.     

Nanorod-pillared mesoporous rGO/ZnO/Au hybrids for photocatalytic Cr (VI) reduction: Enhanced Cr(VI) adsorption and solar energy harvest

Herein, we fabricated mesoporous ternary hybrids composed of Au-functionalized ZnO nanorods grown on rGO nanosheets. The ZnO nanorods distributed on the rGO nanosheets can act as a pillaring layer to avoid the agglomeration of rGO, leading to the formation of abundant mesopores within the hybrids. The high-surface-area, mesoporous hybrids can offer sufficient active sites and transport channels for efficient adsorption and diffusion of Cr(VI), which was favorable for its photocatalytic reduction due to the adsorption enrichment effects. Moreover, the plasmonic-induced visible-light absorption of Au nanoparticles and efficient charge separation by rGO synergistically contributed to the significantly improved solar-light-driven photocatalytic Cr(VI) reduction properties of the ternary hybrids.     

雪花状Cu2S/缺陷型UiO-66 p-n异质结用于光催化还原Cr(VI)

为了解决金属-有机骨架材料Ui O-66可见光响应差、电子-空穴复合快的问题，以雪花状Cu₂S为基材，对Ui O-66进行缺陷调控，采用溶剂热法制得Cu₂S/缺陷型Ui O-66 p-n异质结型复合光催化剂。以K₂Cr₂O₇溶液为目标污染物，分析其对Cr(Ⅵ)的光催化还原能力。SEM、XRD和XPS结果证明，缺陷型UiO-66在雪花状Cu₂S上均匀生长。莫特-肖特基曲线证明，在Cu₂S与缺陷型UiO-66界面处形成了紧密的p-n异质结，提高了材料对可见光的利用率，促进了光生电子-空穴对的有效分离。在模拟可见光照射下，20 mg 50%Cu₂S/缺陷型Ui O-66复合光催化剂(50%为缺陷型UiO-66的负载量，以生成的Cu₂S质量计)对50 mL质量浓度为20 mg/L的K₂Cr₂O₇溶液的还原率高达98.92%，且循环5次...     

The enhanced performance of Cr(VI) photoreduction and antibiotic removal on 2D/3D TiO2/ZnIn2S4 nanostructures

In this study, 2D/3D TiO₂/ZnIn₂S₄ nanostructures with TiO₂ sheet cluster embedded into ZnIn₂S₄ micro flowers were fabricated via hydrothermal method. The matched band structure, the enlarged surface area and the efficient photo-induced charge transfer offered by effective heterostructures formed between the two components endowed the TiO₂/ZnIn₂S₄ nanoarchitecture with excellent photocatalytic Cr(VI) reduction and tetracycline hydrochloride (TC) degradation performance. Especially, the Cr(VI) photoreduction efficiency of 50% TiO₂/ZnIn₂S₄ was 8.8 times higher compared to pure ZnIn₂S₄. The enhanced separation efficiency of photo-excited charge carriers was induced by the matched band structure, the enlarged surface area and the strong interaction between TiO₂ and ZnIn₂S₄. The key roles of ·O₂^? was confirmed via trapping experiments. Otherwise, the pathway of TC degradation was investigated. The proposed mechanism during photocatalysis process was also discussed according to the photocatalytic and characterization results.     

一步水热合成In2S3/CdIn2S4异质结微球及其光催化性能

利用一步水热法成功制备了In₂S₃/CdIn₂S₄异质结微球催化剂,通过降解甲基橙(MO)、酸性橙Ⅱ(AOⅡ) 和罗丹明B(RhB)来评价所制备催化剂的活性。实验结果表明,In₂S₃/CdIn₂S₄异质结微球对MO、AOⅡ和RhB的光催化降解率分别达到了87%、75%和96%,明显高于催化剂In₂S₃和CdIn₂S₄。瞬态光电流和阻抗测试结果表明,In₂S₃/CdIn₂S₄异质结微球受光激发产生的电子空穴对能快速得到分离。捕获主要活性物种实验表明,该反应体系中主要是超氧自由基和空穴起关键性作用。In₂S₃/CdIn₂S₄异质结微球催化剂重复使用四次,其催化能力依然保持较高水平。In₂S₃/CdIn₂S₄异质结微球活性的增强归因于异质结的形成有助于电子的转移,从而降低了电子空穴对的复合概率。并且合适的能带结构有助于产生大量的光生电子,电子与活性氧的结合最终引起氧化能力的增强。     

Gamma irradiated orange peel for Cr(VI) bioreduction

This work presents the γ irradiation (600–3500 kGy) and acid hydrolysis onto orange peel for hexavalent chromium removal. SEM, AFM, TGA-DSC, FTIR, and UV-Vis showed that γ rays enhance degradation and cleavage of orange peel cellulose polymeric chains, increasing the presence of reducing sugars after acid hydrolysis (0.1552 g/g biomass, 3500 kGy). Bioreduction kinetics of Cr(VI) using both solid and solubilized liquid fractions of γ irradiated biomass showed a direct correlation between the applied dose and Cr(VI) removal, reaching 100% of Cr(VI) reduction at pH 2 and 3500 kGy. Cr(VI) reduction is explained as a function of hydrolyzed reducing sugar oxidation.     

Graphene-like h-BN supported polyhedral NiS2/NiS nanocrystals with excellent photocatalytic performance for removing rhodamine B and Cr(VI)

Human health is deteriorating due to the effluent containing heavy metal ions and organic dyes. Hence, photoreduction of Cr(VI) to Cr(III) and degradation of rhodamine B (RhB) using a novel photocatalyst is particularly important. In this work, h-BN/NiS₂/NiS composites were prepared via a simple solvothermal method and a double Z-scheme heterojunction was constructed for efficiently removing RhB and Cr(VI). The 7 wt-% h-BN/NiS₂/NiS composites were characterized via a larger specific surface area (15.12 m²·g^–1), stronger light absorption capacity, excellent chemical stability, and high yield of electrons and holes. The experimental result indicated that the photoreduction efficiency of the 7 wt-% h-BN/NiS₂/NiS photocatalyst achieved 98.5% for Cr(VI) after 120 min, which was about 3 times higher than that of NiS₂/NiS (34%). However, the removal rate of RhB by the 7 wt-% h-BN/NiS₂/NiS photocatalyst reached 80%. This is due to the double Z-scheme heterojunction formed between NiS₂/NiS and h-BN, which improved the charge separation efficiency and transmission efficiency. Besides, the influence of diverse photogenerated electron and hole scavengers upon the photoreduction of Cr(VI) was studied, the results indicated that graphene-like h-BN promoted transportation of photoinduced charges on the surface of the h-BN/NiS₂/NiS photocatalyst via the interfacial effects.     

Anionic precursor-mediated morphology-controlled synthesis of ZnS nanostructures: Morphology-dependent tunable photoluminescence in the visible region and pulsed laser-induced efficient reduction of Cr(VI)

Developing a green and convenient synthesis protocol for modification of the morphology of ZnS nanostructures is of great interest but remains a challenge. Herein, a strategy is proposed for tuning the morphology of ZnS nanostructures using different anionic precursors without addition of any organic surfactants or templates. The role of anionic precursors in determining the morphologies is investigated, and a possible growth mechanism involving oriented aggregation and the Ostwald ripening process is proposed. The as-synthesized ZnS nanostructures exhibit outstanding tunable photoluminescence in the visible region depending on the morphology and excitation wavelength. Additionally, the photocatalytic reduction of aqueous Cr(VI) under pulsed irradiation was studied using ZnS catalysts of various nanostructure morphologies in order to study the influence of morphology on the photocatalytic activity of ZnS nanostructures. The analysis revealed that rice grain-shaped ZnS nanostructures exhibit more efficient photocatalytic Cr(VI) reduction compared to other nanostructures. This work also investigated the dependence of the rate of Cr(VI) reduction on the pulsed laser power, pH, and Cr (VI) concentration. The results presented herein should provide a new approach for designing ZnS nanostructures with different morphologies for application in light emitting diodes (LEDs) and water purification systems.     

Facile one-pot synthesis of a BiOBr/Bi2WO6 heterojunction with enhanced visible-light photocatalytic activity for tetracycline degradation

Photocatalytic removal of tetracycline (TC) from the wastewater is of great value in the chemical and environmental engineering field. Here, we introduced a facile one-step method for the synthesis of BiOBr/Bi₂WO₆ heterojunctions by using cheap CTAB as the Br source. We showed the possibility of our method to fine-tune the content of BiOBr in the produced BiOBr/Bi₂WO₆ by simply changing the dosage of cetyltrimethylammonium bromide (CTAB), providing a platform for the delicate tuning of the visible-light absorbance ability of the composites. With a suitable heterojunction structure of BiOBr/Bi₂WO₆-0.2, it exhibited an ultrarapid photocatalytic activity towards TC (20 mg·L^-1), with a competitive removal efficiency of 88.1% within 60 min and an ultrahigh removal rate of 0.0349 min^-1. It could also be robustly recycled for at least 5 cycles with slight removal efficiency loss. We demonstrated that this exciting photocatalytic performance was due to the highly decreased recombination of photoinduced electrons and holes on our composites by constructing this heterojunction structure, and the resulting OH and contributed to the effective degradation of TC to CO₂.     

WO_3/N-TiO_2异质节可见光催化降解亚甲基蓝

以尿素为氮源,采用溶胶凝胶法制备N掺杂TiO_2,然后与钨酸铵混合研磨,通过高温焙烧的方法原位制备WO_3复合N掺杂TiO_2的异质节光催化材料。分别采用X射线衍射(XRD)、紫外-可见分光光度计(UV-Vis)对样品进行分析,考察样品的光吸收阈值变化。以亚甲基蓝为降解底物,考察了样品的可见光催化处理染料废水效果,结果表明,原位制备的WO_3和N掺杂TiO_2异质节光催化材料对亚甲基蓝表现出良好的可见光催化活性。     

Removal behavior of Cu(II) during Cr(VI) reduction by cast iron powder in absence and presence of ultrasound

ABSTRACT

Cu(II) is an important and typical heavy metal ion in the wastewater containing Cr(VI), and its removal during Cr(VI) reduction by zero valent iron (ZVI) may make it separately be recovered as a kind of copper resource. In this study, the removal behavior of Cu(II) during Cr(VI) reduction by cast iron powder in absence and presence of ultrasound was investigated by atomic absorption spectrometry (AAS), X-ray powder diffractometer (XRD), scanning electron microscope-energy dispersion spectrum (SEM-EDS) and X-ray photoelectron spectroscopy (XPS). The AAS tests indicated that the ultrasound could not only obviously enhance the removal of Cu(II) but also improve the reduction rate of Cr(VI). The XRD and SEM-EDS analyses showed that Cu(II) in the solution was reduced to metallic copper and then was deposited at the surface of ZVI. The ultrasound could remove the Fe-Cr oxides and hydroxides at the ZVI surfaces, resulting in the active surfaces of iron increased. The XPS analyses demonstrated that the surface of metallic copper would be transformed into the film of copper oxide (CuO) in the ultrasound system. The obtained metallic copper and copper oxide could be recovered alone by traditional method of the acid pickling.     

Simultaneous degradation of RhB and reduction of Cr(VI) by MIL-53(Fe)/Polyaniline (PANI) with the mediation of organic acid

MIL-53(Fe)/polyaniline (PANI) composite was prepared by in situ depositing PANI on the surface of MIL-53(Fe) and their catalytic performances on the simultaneous removal of RhB and Cr(VI) were investigated. The elimination efficiency of both RhB and Cr(VI) reached more than 98% under pH=2 where hydrochloric acid and citric acid were used to adjust the pH. The results indicated that MIL-53(Fe)/PANI revealed an obvious pH response to the degradation of RhB, while citric acid promoted the Cr(VI) photoreduction. UV-Vis spectra, EIS, and photocurrent response experiments showed that MIL-53(Fe)/PANI had a better light response and carrier migration ability than MIL-53(Fe). The transient absorption spectra also exhibited that the lifetimes of photo-generated carriers were prolonged after the conductive polymer deposition on the MIL-53(Fe) surface. Scavenger experiments demonstrated that the main active species were ·O₂^- and OH. Combined with activity evaluation results, and the possible photocatalytic mechanism of MIL-53(Fe)/PANI on RhB oxidation and Cr(VI) reduction was proposed. The addition of conductive polymer can effectively improve the light response of the catalyst under acidic conditions, and meanwhile citric acid also provided a new mediation for the synergistic degradation of multiple pollutants. Good activity and stability of the catalysts made the scale-up purification of acid water feasible under UV-Vis light.     

A novel nano-sized MoS2 decorated Bi2O3 heterojunction with enhanced photocatalytic performance for methylene blue and tetracycline degradation

In this paper, MoS₂ was used as a band-suitable semiconductor to construct the Bi₂O₃/MoS₂ heterostructured photocatalysts for the first time via a deposition-hydrothermal method. The XRD, SEM and HRTEM analysis indicated that the surface of Bi₂O₃ was decorated with MoS₂ nanoparticles and Bi₂O₃/MoS₂ heterojunctions were formed. The performances on photocatalytic degradation of methylene blue (MB) and tetracycline (TC) were evaluated under visible light irradiation. The results demonstrated that the Bi₂O₃/MoS₂ heterojunctions displayed remarkably improved photocatalytic activity for both MB and TC degradation, compared to the base material (Bi₂O₃). Specifically, as the molar ratio of MoS₂ was 23.81%, the obtained Bi₂O₃/MoS₂-23.81 heterojunctions exhibited promising photocatalytic activities, and approximately 100% MB and 97% TC were degraded within 100 min, respectively. The superior photocatalytic activity was mainly attributed to its large surface area, high visible-light harvesting and the efficient separation of photogenerated electrons and holes caused by the unique heterojunction architecture. Notably, the Bi₂O₃/MoS₂ heterojunctions showed remarkable stability in recycling photocatatlytic experiments. The active species trapping and terephthalic acid (TA) fluorescence experiments indicated that the •OH was the major reactive oxidizing species for MB degradation. Furthermore, the intermediates were detected by UPLC-MS spectrometry and the possible degradation pathways for MB and TC were proposed. Finally, a possible reaction mechanism of Bi₂O₃/MoS₂ heterojunctions for the photodegradation MB was also proposed. This interesting interfacial architecture strategy will provide useful insights for designing and fabricating new class of binary heterojunctions with high-efficient photocatalytic activity towards practical application.     

Boron-Doped Diamond Electrode Performance in Cr(VI) Reduction Using Synthetic and Plating Wastewater

The goal of this work was to evaluate the effectiveness of iron and boron-doped-diamond (BDD) as cathodic electrodes on the reduction of Cr(VI) in synthetic and wastewater samples. The pH and electrolyte composition were varied, and the effect on the Cr(VI) reduction rate was measured. The optimized conditions from the synthetic water Cr(VI) reduction experimental data, were tasted on electroplating wastewater. The results indicated that both a pH of 2 and the use of NaCl as an electrolyte significantly increase the Cr(VI) reduction rate for all synthetic systems, especially the iron-BDD system. The Cr(VI) reduction rate in Fe-BDD systems was also affected by nitrate and sulfate ions. In the case of electroplating wastewater, Cr(VI) reduction by BDD cathodes was faster than with iron cathodes, achieving a complete reduction of 180 mg Cr(VI)/L in 25 min, with 40% less sludge produced. The elemental composition of sludge was analyzed using SEM/EDS and X-ray spectroscopy to confirm that iron and chromium precipitated out of the solution. The sludge had a chemical composition of (31.9%) Fe₂O₃, (29.6%) FeOOH, (21%) FeO, and (17.4%) FeSO₄. Therefore, BDD as an electrode material effectively reduces Cr(VI) in electroplating wastewater, and can be effectively scaled up to industrial applications.     

Capacity of Cr(VI) reduction in an aqueous solution using different sources of zerovalent irons

Zerovalent iron (ZVI) has drawn intense interest as an effective and inexpensive tool to enhance degradation of various environmental contaminants. Reduction of Cr(VI) to Cr(III) by ZVI merits environmental concern as a hazardous species is transformed into a non-hazardous one. Objectives of this research were to assess kinetics and capacity of Cr(VI) reduction by different sources of ZVIs, of which chemical parameters can base in situ application of ZVI to treat Cr(VI) contaminated water. Reduction kinetics were first-order and rapid showing that 50% of the initial Cr(VI) was reduced within 7.0 to 347 min depending on Cr(VI) concentration, temperature and ZVI source. The reduction rates were increased with decreasing the initial Cr(VI) concentrations and increasing the reaction temperatures. The J ZVI (Shinyo Pure Chemical Co., Japan) was more effective in Cr(VI) reduction than PU (Peerless Metal Powders, USA). The maximum reduction capacities of J and PU ZVIs at 25°C were 0.045 and 0.042 mmol g⁻¹ Fe⁰, respectively. A relatively higher value of the net reaction energy (E _a ) indicated that Cr(VI) reduction by ZVI was temperature dependent and controlled by surface properties of ZVI. Chemical parameters involved in the Cr(VI) reduction by ZVI such as temperature quotient, kinetic rates, and stoichiometry indicated that the ZVI might be effective for in situ treatment of the Cr(VI) containing wastewater.     

A new bioinorganic process for the remediation of Cr(VI)

Palladised biomass of Desulfovibrio desulfuricans ATCC 29577 (bio‐Pd(0)) effected reduction of Cr(VI) to Cr(III) under conditions where biomass alone or chemically‐prepared Pd(0) were ineffective. Reduction of 500 µmol dm^?3 Cr(VI) by 0.4 mg cm^?3 bio‐Pd(0) (Pd : biomass ratio of 1:1) was achieved from 1 mol dm^?3 formate/acetate buffer at pH 1–7 at room temperature; the optimum pH was 3.0. The ratio of mass of Pd : dry mass of biomass, and the need for finely ground bio‐Pd(0) were important parameters for optimal Cr(VI) reduction, with a ratio of 1:1 giving 100% reduction of 500 µmol dm^?3 Cr(VI) within 6 h at room temperature, decreasing to 30 min following heat treatment of the Pd(0)‐loaded biomass. The reduced Cr was recovered quantitatively as soluble Cr(III) at pH 3.0 with no poisoning of the bioinorganic catalyst with respect to continued reduction of Cr(VI). © 2002 Society of Chemical Industry     

Heterocyclic modification of chitosan for the adsorption of Cu (II) and Cr (VI) ions

A heterocyclic modification of chitosan has been attempted for development of an effective adsorbent material for removal of metal ions. The modified polymer was characterized using infrared (IR) spectroscopy, thermogravimetric analysis (TGA), scanning electron microscopy (SEM), energy dispersive x-ray spectroscopy (EDS) and x-ray diffraction (XRD) techniques. The adsorption capacity exhibited for Cu (II) and Cr (VI) were 83.75 and 85.0 mgg^?1, respectively, which is a significant improvement over chitosan. The adsorption on the modified polymer was a second-order kinetic process and followed Langmuir isotherm model. The thermodynamic analysis indicated exothermic and spontaneous nature of adsorption. About 80% of the adsorbed metal ions were desorbed in appropriate stripping solutions indicating reusability.     

Alkali-free synthesis of a novel heterostructured CeO2-TiO2 nanocomposite with high performance to reduce Cr(VI) under visible light

In this study, a novel CeO₂-TiO₂ nanocomposite denoted as CeO₂-3TiO₂ was successfully synthesized via a facile one pot hydro-thermal method without alkali. It exhibits high photocatalytic reduction reactivity toward Cr(VI) under visible light. The photocatalytic reactivity of CeO₂-3TiO₂ is 18 times higher than that of pure CeO₂, 28 times higher than pure TiO₂, 15 times higher than the sample of simply mixed CeO₂ and TiO₂. The solution with Cr(VI) initial concentration of 2780 ppb can be fast photoreduced by CeO₂-3TiO₂ in 60 min under visible light to meet the criterion of U.S. Environmental protection Agency. Characterization results indicate CeO₂-3TiO₂ has the good crystal form of heterojunction structure, narrow pore size distribution, narrow energy gap and high photogenerated electron-hole separation efficiency. Based on the experimental results, a speculated photocatalytic mechanism was proposed.