State-of-the-art technology: Recent investigations on laser-mediated synthesis of nanocomposites for environmental remediation

In both developing and industrialized/developed countries, various hazardous/toxic environmental pollutants are entering water bodies from organic and inorganic compounds (heavy metals and specifically dyes). The global population is growing whereas the accessibility of clean, potable and safe drinking water is decreasing, leading to world deterioration in human health and limitation of agricultural and/or economic development. Treatment of water/wastewater (mainly industrial water) via catalytic reduction/degradation of environmental pollutants is extremely critical and is a major concern/issue for public health. Light and/or laser ablation induced photocatalytic processes have attracted much attention during recent years for water treatment due to their good (photo)catalytic efficiencies in the reduction/degradation of organic/inorganic pollutants. Pulsed laser ablation (PLA) is a rather novel catalyst fabrication approach for the generation of nanostructures with special morphologies (nanoparticles (NPs), nanocrystals, nanocomposites, nanowires, etc.) and different compositions (metals, alloys, oxides, core-shell, etc.). Laser ablation in liquid (LAL) is generally considered a quickly growing approach for the synthesis and modification of nanomaterials for practical applications in diverse fields. LAL-synthesized nanomaterials have been identified as attractive nanocatalysts or valuable photocatalysts in (photo)catalytic reduction/degradation reactions. In this review, the laser ablation/irradiation strategies based on LAL are systematically described and the applications of LAL synthesized metal/metal oxide nanocatalysts with highly controlled nanostructures in the degradation/reduction of organic/inorganic water pollutants are highlighted along with their degradation/reduction mechanisms.     

Photocatalytic degradation of methylene blue and sulfisoxazole from water using biosynthesized zinc ferrite nanoparticles

The extensive occurrence of textile and pharmaceutical contaminants and their metabolites in water systems has posed significant concerns regarding their possible threat to human health and the environmental system. As a result, herein ZnFe₂O₄ nanoparticles were synthesized through the use of Monsonia burkeana plant extract. The synthesized nanoparticles were characterized using XRD, FTIR, UV–vis, SEM, EDS, TGA, BET, PL, EPR and VSM. XRD showed that the crystalline structure of ZnFe₂O₄ nanoparticles with a calculated crystal size of 25.03 nm was formed. FT-IR confirmed the characteristic functional groups contained within the M. burkeana plant were deposited on the formed ferrite nanoparticles. BET analysis confirmed the mesoporous nature of ZnFe₂O₄ with an average pore diameter of 31.6 nm. Morphological studies demonstrated that the formed nanoparticles had spherical as well as rod-like shapes. ZnFe₂O₄ photocatalyst illustrated that it may be effortlessly detached by an external magnetic field. The optimum conditions for the 99.8% removal of Methylene Blue was obtained at pH12, within 45min and at the optimum dosage of 25 mg of the catalyst. The as-prepared ZnFe₂O₄ nanoparticles proved to be easily separated and recycled, and remained efficient even after 5 reuses, proving that the material is highly stable. The ROS studies also demonstrated that electrons are the main factors contributing to the degradation of MB. Upon testing the photocatalytic performance of the sulfonamide antibiotic, sulfisoxazole in water showed a degradation of 67%. This study has shown that these materials can be used in targeting textile and pharmaceutically polluted water.     

Synthesis of magnetically recyclable porous CoFe2O4/Rh composites with large BET surface area for enhanced photocatalytic degradation of organic pollutant

The organic pollutants in water have been a great environment challenges to human beings, and photocatalytic degradation is an effective method to solve this problem. In this paper, the Rh-loaded cobalt ferrite CoFe₂O₄ (CFO) nanoparticles have been successfully synthesized by in situ photodeposition of Rh nanoparticles onto the porous CFO particles as the photocatalysts. After incorporating Rh nanoparticles, the CFO/Rh composite has a higher specific surface area and is more efficient in charge separation than the bare CFO. The photocatalytic efficiency of decomposing Malachite Green (MG) is improved from 70% over the bare CFO to 97% over the optimized CFO/Rh in 60 min. The CFO/Rh sample also demonstrates its durability for the degradation of MG in 5 photocatalytic reaction cycles. Additionally, hydroxyl radicals (?OH) and superoxide radicals (?O₂^?) are proved to be the crucial reactive species during the photocatalytic degradation of MG with CFO/Rh, evidenced by the active species capture experiments. This work provides a useful approach to enhance the photocatalytic activity of semiconductors for degrading organic dyes.     

Enhanced the photocatalytic activity of B–C–N–TiO2 under visible light:Synergistic effect of element doping and Z-scheme interface heterojunction constructed with Ag nanoparticles

In order to enhance the photocatalytic activity of TiO₂ under visible light, Ag nanoparticles were introduced into tridoped B–C–N–TiO₂ (TT) catalyst by photoreduction deposition. Ag/B–C–N–TiO₂ (ATT) catalysts with the functions of reducing band gap and carrier recombination were prepared. At the same time, the effect of the amount of Ag on the photocatalytic performance of ATT catalyst was investigated. Through XRD, XPS, PL and other characterization methods, the (211)/(101)/Ag interface heterojunction mechanism similar to the traditional Z-scheme heterojunction was proposed. The intervention of Ag nanoparticles changed the P–N interface heterojunction between (211)/(101) to the (211)/(101)/Ag Z-scheme interface heterojunction. The results show that ATT catalyst exhibits the highest photocatalytic activity when the molar amount of Ag is 0.005% with the MB degradation rate of the ATT catalyst (0.01707 min^?1), which is 14.59 times of TiO₂ (0.00117 min^?1) and 2.02 times of TT (0.00847 min^?1). In addition, the four cycles efficiencies of ATT for MB degradation were all above 94.00%.This study reveals the possibility of construction of Z-scheme heterojunctions between precious metal nanoparticles and different interfaces of TiO₂, and provides a reference for the construction of Z-scheme interface heterojunctions.     

Construction,structure and photocatalysis of janus nanofiber modified by g-C3N4 nanosheets heterostructure photocatalysts

The construction of photocatalyst with gradient band structure is guided by the principle of band gap engineering. Rational structural design is advanced and applied to construct a new-typed peculiarly structural and functional carbon-based [TiO₂/C]//[Bi₂WO₆/C] Janus nanofiber modified by g-C₃N₄ nanosheets heterostructure photocatalyst (denoted as TB-JgHP). The flexible carbon-based [TiO₂/C]//[Bi₂WO₆/C] Janus nanofiber with one side responding to ultraviolet light and the other capturing visible light is fabricated by conjugate electrospinning, and then g-C₃N₄ nanosheets are uniformly grown in-situ on the surface of the Janus nanofibers by using gas-solid reaction via gasification of urea. The optimized TB-JgHP possesses remarkable hydrogen evolution efficiency (17.48 mmol h⁻¹ g⁻¹) and methylene blue degradation rate (99.2%) under simulated sunlight illumination for 100 min, demonstrating prominent dual-functional characteristics. The enhanced photocatalytic performance benefits from the unique Janus structure as well as the synergistic effects among the triple heterostructures of TiO₂ and Bi₂WO₆, g-C₃N₄ and TiO₂, g-C₃N₄ and Bi₂WO₆. The formation of gradient band structure among heterostructures is more conducive to the multi-step separation of photo-induced electron-hole pairs and more effective absorption of light. Further, flexible self-standing carbon-based photocatalysts not only have outstanding electron transport performance, but also are easy to separate from solution with preeminent recyclable stability. Based on a series of characterization techniques, it is further proved that TB-JgHP has higher carrier separation efficiency than the counterpart contrast samples. The formation mechanism of TB-JgHP is proposed, and the construction technique is established. The design philosophy and construction technique presented in this work pave a new avenue for research and development of other heterostructure photocatalysts.     

Hydrophobic Cross-Linked Poly(dimethylsiloxane)-Based Sorbents for Oil Spill Applications

With the increase of industrialization and urbanization, humankind faces massive oil-based pollution due to tanker accidents, human error, and natural disasters. For this, hydrophobic sorbents are fabricated and their applications for the removal of oil from polluted water sources are investigated. These hydrophobic sorbents are prepared by the condensation reaction of poly(dimethylsiloxane) and tris[3-(trimethoxysilyl)propyl]isocyanurate cross-linker via bulk polymerization. The obtained sorbents exhibit high oil sorption capacity, fast absorption–desorption kinetics, and great reusability. Moreover, they can selectively absorb oil from the water surface, thus making them practical for water clean-up applications.     

Kinetic analysis of crystallization of zeolite beta synthesized by direct heating

To quantitatively investigate the initial crystallization of zeolite beta synthesized by direct heating, the extent of the reaction was precisely evaluated by X-ray diffraction measurements and Rietveld structural refinement, and a kinetic analysis of crystallization was performed using the Avrami-Erofe'ev equation. The activation energy for crystallization was lower than that for hydrothermal synthesis. Reaction and synthesis time curves revealed that the initial zeolite beta crystallization consisted of three stages. The first was an induction period with nucleation by the generation of building units and the formation of an initial coordinated structure. The second stage was crystal growth by a diffusion-controlled reaction, and the third stage involved slowing down of crystallization by the limitation of dehydrocondensation. These stages could be analyzed by calculation of the rate constant and Avrami exponent for each stage.     

Strong tribocatalytic dye degradation by tungsten bronze Ba4Nd2Fe2Nb8O30

The triboelectric effect has recently demonstrated its great potential in environmental remediation and even new energy applications for triggering a number of catalytic reactions by utilizing trivial mechanical energy. In this study, Ba₄Nd₂Fe₂Nb₈O₃₀ (BNFN) submicron powders were used to degrade organic dyes via the tribocatalytic effect. Under the frictional excitation of three PTFE stirring rods in a 5 mg/L RhB dye solution, BNFN demonstrates a high tribocatalytic degradation efficiency of 97% in 2 h. Hydroxyl radicals (?OH) and superoxide radicals (?O₂－) were also detected during the catalysis process, which proves that triboelectric energy stimulates BNFN to generate electron-hole pairs. The tribocatalysis of tungsten bronze BNFN submicron powders provides a novel and efficient method for the degradation of wastewater dye by utilizing trivial mechanical energy.     

New insights into the mechanisms of carbon dioxide mineralization by portlandite

Portlandite (Ca(OH)₂; also known as calcium hydroxide or hydrated lime), an archetypal alkaline solid, interacts with carbon dioxide (CO₂) via a classic acid–base “carbonation” reaction to produce a salt (calcium carbonate: CaCO₃) that functions as a low-carbon cementation agent, and water. Herein, we revisit the effects of reaction temperature, relative humidity (RH), and CO₂ concentration on the carbonation of portlandite in the form of finely divided particulates and compacted monoliths. Special focus is paid to uncover the influences of the moisture state (i.e., the presence of adsorbed and/or liquid water), moisture content and the surface area-to-volume ratio (s_a/v, mm⁻¹) of reactants on the extent of carbonation. In general, increasing RH more significantly impacts the rate and thermodynamics of carbonation reactions, leading to high(er) conversion regardless of prior exposure history. This mitigated the effects (if any) of allegedly denser, less porous carbonate surface layers formed at lower RH. In monolithic compacts, microstructural (i.e., mass-transfer) constraints particularly hindered the progress of carbonation due to pore blocking by liquid water in compacts with limited surface area to volume ratios. These mechanistic insights into portlandite's carbonation inform processing routes for the production of cementation agents that seek to utilize CO₂ borne in dilute (≤30 mol%) post-combustion flue gas streams.     

Antibacterial and photocatalytic behaviour of green synthesis of Zn0.95Ag0.05O nanoparticles using herbal medicine extract

The present work aimed to synthesize Zn_0.95Ag_0.05O (ZnAgO) nanoparticles using rosemary leaf extracts as a green chemistry method. The characterization of Ag-doped ZnO nanoparticles was performed by Fourier transform infrared spectroscopy (FTIR), X-ray diffraction (XRD), field emission scanning electron microscopy (FESEM), and ultraviolet–visible spectrophotometry (UV–visible). The XRD, FTIR, and UV–visible spectra confirmed the formation of the presence of hexagonal ZnAgO nanoparticles. FESEM micrograph shows that the nanoparticles have been distributed homogeneously and uniformly. The morphology of ZnAgO nanoparticles is quasi-spherical configuration. Also, the mean particle size is in the range of 22–40 nm. The photocatalytic degradation of methylene blue in the presence of Ag-doped ZnO nanoparticles is nearly 98.5% after exposing 100 min. The ultraviolet lamp was used as the light source for photocatalyst degradation. The disc diffusion method was chosen to study the antibacterial activity of as-synthesized ZnAgO nanoparticles. Antibacterial activity of Zn_0.95Ag_0.05O nanoparticles against Staphylococcus aureus and Escherichia coli revealed that the as-synthesized ZnAgO nanoparticles were efficient in inhibition of bacterial growth.