CdBiO2Br nanosheets in situ strong coupling to carbonized polymer dots and improved photocatalytic activity for organic pollutants degradation

Carbonized polymer dots (CPDs) modified layer-structured CdBiO₂Br (CPDs/CdBiO₂Br) Z-scheme heterojunction hybrid material has been synthesized via simple solvothermal method. The hybrid material with Z-scheme heterojunction can effectively maintain the original highly oxidizing holes of CdBiO₂Br and the highly reducing electrons of CPDs. In addition, the construction of heterostructure is beneficial to the migration and separation of photogenerated carriers. Under visible light irradiation, 6 wt% CPDs/CdBiO₂Br showed the best catalytic activity for degradation of organic pollutants. Free radical capture experiments and ESR analysis confirmed that the main active species are ^?O₂^? and h⁺. The decomposition process of organic pollutants was analyzed by LC-MS. Finally, the probable visible light mechanism performance of CPDs/CdBiO₂Br as direct Z-scheme heterojunction photocatalytic materials was proposed.     

NiCo2O4/BiOCl/Bi24O31Br10 ternary Z-scheme heterojunction enhance peroxymonosulfate activation under visible light: Catalyst synthesis and reaction mechanism

The Z-scheme heterostructure for photocatalyst can effectively prolong the lifetime of photogenerated carriers and retain a higher conduction/valence band position, promoting the synergistic coupling of photocatalysis and peroxymonosulfate (PMS) activation. In order to fully utilize the luminous energy and realize the efficient activation of PMS, this work achieved successful construction of NiCo₂O₄/BiOCl/Bi₂₄O₃₁Br₁₀ ternary Z-scheme heterojunction by simultaneously synthesizing BiOCl and NiCo₂O₄ with NiCl₂ and CoCl₂ as the precursors. The intercalated BiOCl could serve as a carrier migration ladder to further achieve the spatial separation of electron-hole pairs, so that the oxidation and reduction processes separately occurred in different regions. Compared with the reported catalysts, the as-prepared composites exhibited the enhanced removal efficiency for tetracycline hydrochloride (TCH) in the visible light/PMS system, with a degradation efficiency of 85.30% in 2 min, and possessed good stability. Z-scheme heterojunction was shown to be beneficial for maximizing the superiority of photo-assisted Fenton-like reaction system. The experimental and characterization results confirmed that both non-radicals (¹O₂) and radicals (SO₅^?? and SO₄^??) were involved in the reaction process and the SO₅^?? generated by the oxidation of PMS played a crucial role in the TCH degradation. The possible reaction mechanism was finally proposed. This study provided new insight into the Z-scheme heterostructure to promote the photo-assisted Fenton-like reaction.     

Photocatalytic removal of tetracycline by a Z-scheme heterojunction of bismuth oxyiodide/exfoliated g-C3N4: performance,mechanism, and degradation pathway

Antibiotics, once being released into the environment, become recalcitrant organic pollutants, which pose a potential risk to ecological balance and human health. In this study, a Z-scheme heterojunction of bismuth oxyiodide (BiOI)/exfoliated g-C₃N₄ (BiOI/ECN hereafter) was synthesized by the combination of thermal exfoliation of g-C₃N₄ and chemical precipitation of BiOI for efficient photocatalytic degradation of tetracycline in aqueous solutions under visible light irradiation. The optimized BiOI/ECN delivered an outstanding degradation rate at circa 0.0705 min^?1, which was 10 times higher than that of the bulk g-C₃N₄. The photocatalytic degradation efficiency of tetracycline remained almost unchanged in a pH range of 3–11, and the BiOI/ECN displayed an excellent photostability upon recycled usage. The photocatalytic mechanism of tetracycline was ascribed to the main reactive oxidation species of photogenerated holes and superoxide radicals. In addition, the possible degradation pathways of tetracycline were investigated by HPLC-MS to identify intermediates. The toxicity of photocatalytic-generated intermediates of tetracycline was found significantly alleviated according to the calculation of quantitative structure–activity relationship prediction. This work not only provides an attractive photocatalyst for the removal of tetracycline but also opens a new avenue for rational design of Z-scheme heterojunction composites for tetracycline degradation.     

Construction of direct Z-scheme g-C3N4/TiO2 nanorod composites for promoting photocatalytic activity

Direct Z-scheme g-C₃N₄/TiO₂ nanorod composites were prepared for enhancing photocatalytic activity for pollutant removal. The characterization revealed that the g-C₃N₄/TiO₂ nanorod composite formed a close interface contact between g-C₃N₄ and TiO₂ nanorods, which was of benefit for the charge transfer and resulted in its high photocatalytic activity. The g-C₃N₄/TiO₂ nanorod composites exhibited higher photocatalytic activity for degradation of Rhodamine B (RHB) than bare g-C₃N₄ and TiO₂ nanorods. The high photocatalytic activity of g-C₃N₄/TiO₂ nanorod composites is attributed to the formation of the direct Z-scheme system, in which the electrons from the conduction band (CB) of TiO₂ combine with the holes from the valence band (VB) of C₃N₄ while the electrons from the CB of C₃N₄ and holes from the VB of TiO₂ with stronger redox ability are used to reduce and oxidize pollutants. Based on the radical-trapping experiments, the main reactive species for RHB degradation are O₂⁻ and · OH, which are produced by photoinduced electrons and holes with high redox ability. This work provides insights into the photocatalytic mechanism of composite materials for the photocatalytic removal of organic pollutants.     

Heterojunction architecture of Nb2O5/g-C3N4 for enhancing photocatalytic activity to degrade organic pollutants and deactivate bacteria in water

Water pollution has become a serious problem owing to the development of society. Photocatalysis is a promising approach to remove various pollutants in water, such as organic pollutants and antibiotic resistance bacteria. Meanwhile, the design of heterojunction between two semiconductors is an effective path to improve photocatalytic properties due to its potential in improving separation and transfer of photoinduced carriers. In this study, Nb₂O₅/g-C₃N₄ (NO/CN) composite materials were prepared through a one-step heating method. Characterizations confirmed successful preparation of NO/CN heterojunction structure and better optical properties than pure g-C₃N₄ and Nb₂O₅. NO/CN composite materials showed excellent photocatalytic efficiency for Escherichia coli (E. coli) inactivation (95%) compared with the pure Nb₂O₅ (10%) and g-C₃N₄ (77%). Meanwhile, NO/CN exhibited better organic pollutants removal (RhB for 94%, methyl orange (MO) for 15% and methylene blue (MB) for 87%) under visible light, which is likely owing to the heterojunction structure between g-C₃N₄ and Nb₂O₅ that leads to the good separation of photogenerated electron-hole pair. Free radical scavenging and electron spin resonance (ESR) experiments demonstrated that superoxide radicals (^?O₂^?) and holes (h⁺) were the dominant radicals. Therefore, the NO/CN was proposed to be a promising material for effective disinfection and removal of organic contaminants in water treatment.     

The preparation of new palladium (II) complexes with Schiff base type ligands and its impregnated Al2O3 materials: As the catalysts for degradation/reduction of organic dyes

The removal of organic dyes used in many sectors such as textile, paper, leather, and packaging from water sources is very important in terms of preventing the spread of industrial pollutants to the environment. Transition metal complexes supported to an inorganic solid material are frequently used for the degradation/reduction of organic dyes causing this pollution. In this study, new Pd (II) complexes with Schiff base ligands were synthesized and structurally characterized by nuclear magnetic resonance (NMR), Fourier-transform infrared spectroscopy (FT-IR), mass spectrometry (MS), and single-crystal X-ray diffraction (sc-XRD) spectroscopic methods. Then, the Al₂O₃-impregnated materials of these Pd (II) complexes were prepared and characterized by scanning electron microscopy with energy dispersive X-ray analysis (SEM-EDX), FT-IR, and thermogravimetry (TG) techniques. The catalytic activities of the synthesized Pd (II) complexes and their Al₂O₃-impregnated materials were comparatively analyzed to investigate the degradation/reduction of organic dyes (2-nitroaniline, 4-nitroaniline, 4-nitrophenol, eosin yellow, and methylene blue). The catalytic results indicate that Al₂O₃-impregnated materials are very active catalysts for the degradation/reduction of organic dyes under those circumstances. Conversions of up to 98% for all substrates were obtained after 5 min at ambient temperature.     

Facile and green synthesis of Cu3V2O8 nanostructures via Moringa peregrina natural extract as a high performance photo catalyst

In this paper Cu₃V₂O₈ nanoparicles were synthesized with a low-cost and green method with using the extract of Moringa peregrine. This novel synthesized material was characterized by using X-ray diffraction (XRD), Field emission scanning electron microscopy (FESEM) and Energy-dispersive X-ray spectroscopy (EDS) analysis. The analysis showed the produced nanoparticles have high purity and well crystalline structure. Moreover, the capability of the nanostructures for the removal of dye pollutants was evaluated. For this purpose, methylene blue was selected as a model of organic dye. The experiments showed Cu₃V₂O₈ nanoparticles have high efficiency for removing of dye molecules. Photocatalytic decolorization of methyl blue was optimized with varying the experiment conditions. With 0.02 g of catalyst, pH 6 and concentration of dye 30 mg/l removal efficiency was obtained about 90% in a short time 20 min. Also a kinetic study showed this photodegradation process obeys a first-order kinetic with rate constant about 0.07 min⁻¹.     

CoFe2O4 with MoS2-xOy Nanosheets as a Co-catalyst for Enhanced Activation of Peroxydisulfate in Advanced Oxidation Processes

The application of advanced oxidation processes (AOPs) based on sulfate radicals for degrading persistent organic pollutants faces challenges due to the inefficient activation of peroxydisulfate (PDS) oxidant. Herein, a composite CoFe₂O₄/MoS_2-xO_y (CFM) catalyst consisting of CoFe₂O₄ nanoparticles uniformly dispersed on the nanosheets of oxygen-incorporated MoS₂ (MoS_2-xO_y) with flower-like morphology are fabricated through a facile two-step hydrothermal method, which results in the enhanced activation of PDS and a highly efficient degradation of phenolic pollutants. The oxygen-doping in MoS_2-xO_y leads to unsaturated sulfur and active sites on the surface of MoS₂ for accelerating the rate limiting step of Fe^III/Fe^II reduction cycle in PDS-CFM reaction. Aiming at the refractory organic pollutants in actual coking wastewater, CFM co-catalyst is introduced into a hydrogel made up of polyvinyl alcohol (PVA) and coal-tar pitch oxides (PO) to construct a multifunctional CFM@PO/PVA hydrogel. Upon hybrid CFM@PO/PVA, the coupling of the enhanced AOP with solar-driven interfacial vapor generation (SIVG) technology contributes to the degradation efficiency, the removal rate of phenol in solution and the total organic carbon in coking wastewater can reach 98 % and 91 %, respectively. The integration of heterogeneous AOPs with SIVG system provides a feasible strategy for the eco-friendly efficient purification of industrial wastewater.     

Fabrication of Cs2.5H0.5PW12O40 three-dimensional ordered film by colloidal crystal template

A three-dimensional ordered polyoxometalate periodic film was synthesized using dodecatungstophosphoric acid (H₃PW₁₂O₄₀) and Cs₂CO₃ as precursors and colloidal crystals as templates by an inverse opal method. The samples were characterized by elemental analysis, XRD, IR spectra, UV-Vis diffuse reflectance spectra (DR-UV-Vis) and SEM techniques. This arrayed film constructed by pure cesium salt of dodecatungstophosphoric acid Cs_2.5H_0.5PW₁₂O₄₀ nanoparticles shows well-defined lamellar array with inverse opal structure, which exhibits a well-defined photonic band gap.     

Preparation and characterization of Pb<Subscript>0.56</Subscript>Sr<Subscript>0.44</Subscript>Zr<Subscript>0.52</Subscript>Ti<Subscript>0.48</Subscript>O<Subscript>3</Subscript> inverse opal

Pb_0.56Sr_0.44Zr_0.52Ti_0.48O₃ (PSZT) inverse opal photonic crystals (PCs) have been synthesized by a process of self-assembly in combination with a sol–gel procedure. PSZT inverse opals show pure perovskite structure with good orders in three dimensions. The evident photonic band gaps have been observed in the transmittance spectra with a blue-shift phenomenon due to the decrease of opal template periods. PSZT inverse opals also exhibit the reflection peaks in basic agreement with the calculated results. This three-dimensional (3D) ordered PSZT inverse opals have shown interesting optical characteristics and potential applications in optoelectronic and photonic devices.     

Cooperative coupling of photocatalytic production of H2O2 and oxidation of organic pollutants over gadolinium ion doped WO3 nanocomposite

This work reported the lanthanide ion (Gd³⁺) doped tungsten trioxide (Gd-WO₃) nanocrystal for remarkable promoted photocatalytic degradation of organic pollutants and simultaneous in-situ H₂O₂ production. With doped lanthanide ion (Gd³⁺), Gd-WO₃ showed a much broad and enhanced solar light absorption, which not only promoted the photocatalytic degradation efficiency of organic compounds, but also provided a suitable bandgap for direct reduction of oxygen to H₂O₂. Additionally, the isolated Gd³⁺ on WO₃ surface can efficiently weaken the *OOH binding energy, increasing the activity and selectivity of direct reduction of oxygen to H₂O₂, with a rate of 0.58 mmol L⁻¹ g⁻¹ h⁻¹. The in-situ generated H₂O₂ can be subsequently converted to ^•OH based on Fenton reaction, further contributed to the overall removal of organic pollutants. Our results demonstrate a cascade photocatalytic oxidation-Fenton reaction which can efficiently utilize photo-generated electrons and holes for organic pollutants treatment.     

Review on augmentation in photocatalytic activity of CoFe2O4 via heterojunction formation for photocatalysis of organic pollutants in water

In previous years, cobalt ferrite has gained huge consideration in the field of semiconductor photocatalysis for waste water treatment. Cobalt ferrite and its derivatives own tunable magnetic properties which results in higher absorption capability in comparison with other photocatalyst semiconductors. In the current review, a brief overview of CoFe₂O₄ as a semiconductor photocatalyst is presented and ferromagnetic behaviour of CoFe₂O₄ is also discussed. Few drawbacks such as agglomeration, photocorrosion and recombination rate of electrons-holes are also discussed. For the enhancement of photocatalytic action of cobalt ferrite, the role of cobalt ferrite with type I, type II, direct Z-scheme, solid state Z-scheme heterojunctions, Schottky and p-n heterojunctions based on different heterostructures were also discussed. In conclusive outlook formation of cobalt ferrite based heterojunctions is best approach for the enhancement of photocatalytic performance. This is because heterojunction formation enhanced the rate of charge separation and thus reduced the electron–hole recombination. Herein, this review highlights the CoFe₂O₄ based heterojunctions for the photodegradation of noxious organic pollutants in water. Furthermore, the future expectations and challenges in exploiting CoFe₂O₄ nanocomposites for water treatment, also discussed in precise conclusion of this review.     

Photocatalytic degradation of organophosphate flame retardant TBEP: kinetics and identification of transformation products by orbitrap mass spectrometry

The photocatalytic degradation of tris (2–butoxyethyl) phosphate (TBEP) flame retardant using visible light response catalysts TiO₂/V₂O₅, (N,F-doped)-TiO₂/V₂O₅, and N-doped-SrTiO₃ has been studied by high-resolution orbitrap mass spectrometry. TBEP degradation followed first-order kinetics with half-life values ranging between 9.8 and 83.5 min. N-doped-SrTiO₃ was the catalyst with better photocatalytic performance while activity for TiO₂/V₂O₅ composites followed the trend: N, F- TiO₂/V₂O₅ > N-TiO₂/V₂O₅> TiO₂/V₂O₅. The identified degradation products (DPs) revealed hydroxylation, further oxidation and dealkylation as major degradation pathways. Based on the identified DPs and scavenging experiments, ^?OH radical-mediated reactions can be considered for the degradation of TBEP using TiO₂ and SrTiO₃-based photocatalytic materials.     

A Z‐Scheme‐Inspired Photobioelectrochemical H2O/O2 Cell with a 1 V Open‐Circuit Voltage Combining Photosystem II and PbS Quantum Dots

A biohybrid photobioanode mimicking the Z‐scheme has been developed by functional integration of photosystem II (PSII) and PbS quantum dots (QDs) within an inverse opal TiO₂ architecture giving rise to a rather negative water oxidation potential of about ?0.55 V vs. Ag/AgCl, 1 m KCl at neutral pH. The electrical linkage between both light‐sensitive entities has been established through an Os‐complex‐modified redox polymer (P_Os), which allows the formation of a multi‐step electron‐transfer chain under illumination starting with the photo‐activated water oxidation at PSII followed by an electron transfer from PSII through P_Os to the photo‐excited QDs and finally to the TiO₂ electrode. The photobioanode was coupled to a novel, transparent, inverse‐opal ATO cathode modified with an O₂‐reducing bilirubin oxidase for the construction of a H₂O/O₂ photobioelectrochemical cell reaching a high open‐circuit voltage of about 1 V under illumination.     

Oriented free-standing ammonium vanadium oxide nanobelt membranes: highly selective absorbent materials

Highly selective, absorbent, free‐standing, paper‐like membranes made of ammonium vanadium oxide (NH₄V₄O₁₄) nanobelts have been engineered by taking advantage of the nanoscaled self‐assembly of architectures that display a mesh structure with an average periodic pore size of about 5 to 10 nm. The NH₄V₄O₁₄ nanobelts are synthesized by using a simple hydrothermal process, and exhibit the same orientation and assemble into bundles, each about 40 to 80 nm in width, 3 to 5 nm in thickness, and up to several millimeters in length. Importantly, the as‐obtained NH₄V₄O₁₄ nanobelt membranes can highly selectively absorb a variety of organic solvents, covering both polar and non‐polar solvents, for example, the absorbent capacity of glycol is 28 times as high as the initial weight of the membrane, and it can even separate organic solvents with similar polarities and absorb solid contaminants in organic solvents. These highly selective, absorbent membrane materials can be an ideal candidate for the separation and removal of pollution in industrial and environmental applications.     

二氧化钛反蛋白石薄膜的制备及其在化学传感器中的应用

用提拉成膜法将单分散295 nm聚甲基丙烯酸甲酯(PMMA)胶体微球自组装成蛋白石光子晶体膜. 在PMMA蛋白石光子晶体膜的空隙里填充15 nm二氧化钛纳米颗粒, 经500 ℃的处理除去PMMA膜板, 制备出大面积, 结构均一的二氧化钛反蛋白石光子晶体膜. 扫描电子显微镜(SEM)观察和X射线光电能谱(XPS)分析表明, 这种二氧化钛反蛋白石光子晶体薄膜是六方紧密堆积. 用这种二氧化钛反蛋白石光子晶体膜对溶液折射率的检测实验表明该传感膜分辨率可达0.01.     

Removal of Model Pollutants in Aqueous Solution by Gliding Arc Discharge: Determination of Removal Mechanisms. Part I: Experimental Study

The respective roles of short and long-life oxidant species in the degradation of model organic pollutants in water have been investigated in a gas–liquid gliding arc plasma reactor. Three different model pollutants were treated in two configurations: direct discharge mode and spatial post discharge mode. In each case the pollutants were classified according to their ease of removal, from easier to more difficult to remove. The results were as follows: phenol >> 1-heptanol >> pCBA. The removal mechanisms also are different depending on the characteristics of the pollutant treated. Phenol (100 % of phenol was removed for energy density = 1.20 × 10⁵ J/L) was supposed to react strongly with NO₂° radicals produced by the dissociation of N₂O₄ in liquid phase. The degradation of 1-heptanol would proceed by desorption of the liquid phase to the gas phase, where oxidation occurs due to the plasma active short-lived species. In the case of pCBA, oxidation occurs in the liquid solution, but the degradation is low because of its low reactivity with species such as ozone and °NO₂ and insufficient production of OH° radicals in the solution.     

Highly dispersed Mn2O3−Co3O4 nanostructures on carbon matrix as heterogeneous Fenton-like catalyst

This work reports the synthesis of various carbon (Vulcan XC-72 R) supported metal oxide nanostructures, such as Mn₂O₃, Co₃O₄ and Mn₂O₃−Co₃O₄ as heterogeneous Fenton-like catalysts for the degradation of organic dye pollutants, namely Rhodamine B (RB) and Congo Red (CR) in wastewater. The activity results showed that the bimetallic Mn₂O₃−Co₃O₄/C catalyst exhibits much higher activity than the monometallic Mn₂O₃/C and Co₃O₄/C catalysts for the degradation of both RB and CR pollutants, due to the synergistic properties induced by the Mn−Co and/or Mn (Co)−support interactions. The degradation efficiency of RB and CR was considerably increased with an increase of reaction temperature from 25 to 45°C. Importantly, the bimetallic Mn₂O₃−Co₃O₄/C catalyst could maintain its catalytic activity up to five successive cycles, revealing its catalytic durability for wastewater purification. The structure–activity correlations demonstrated a probable mechanism for the degradation of organic dye pollutants in wastewater, involving •OH radical as well as Mn²⁺/Mn³⁺ or Co²⁺/Co³⁺ redox couple of the Mn₂O₃−Co₃O₄/C catalyst.     

Facile synthesis of Z-scheme NiO/α-MoO3 p-n heterojunction for improved photocatalytic activity towards degradation of methylene blue

In this article, Z-scheme NiO/α-MoO₃ p-n heterojunction is successfully synthesized by a facile hydrothermal route. The phase and nanostructures are researched through a series of characterizations, such as XRD, SEM, TEM, EDX, XPS and DRS. It is confirmed that the NiO nanoparticles are deposited homogeneously on one dimensional α-MoO₃ nanobelts and p-n heterojuction is constructed at the interface of α-MoO₃ and NiO. Photocatalytic activity of the as-synthesized photocatalysts is investigated by photodegradation of methylene blue (MB) under simulated solar light irradiation. Compared with bare α-MoO₃, the NiO/α-MoO₃ p-n heterojunction exhibits significantly improved photocatalytic activity and photostability for MB degradation. The improvement in the photocatalytic performance can be attributed to the optimization of the charge transport pathway offered by Z-scheme heterojunctions, which can promote the effective separation of electron-hole pairs. The results indicate that Z-scheme NiO/α-MoO₃ p-n heterojunction is a novel and efficient photocatalyst with potential application for the removal of organic contaminant in wastewater.     

A New Method for the Production of Carbon Nanotubes

It was found for the first time that carbon nanotubes are formed during the mechanical treatment of V₂O₅ powder in the presence of an organic solvent. The carbon content in the V₂O₅ sample, dispersed in alcohol, varies during milling and amounts to 2.1 wt.%. The unusually large increase in the catalytic activity of mechanically activated V₂O₅ in the selective oxidation of n-butane and also of benzene and propane is due to the formation of new active centers containing carbon inserted into the V₂O₅ structure.