A facile method for preparing the CeMnO3 catalyst with high activity and stability of toluene oxidation: The critical role of small crystal size and Mn3+-Ov-Ce4+ sites.

Volatile organic compounds (VOCs) cause severe environmental pollution and are potentially toxic to humans who have no defense against exposure. Catalytic oxidation of these compounds has thus become an interesting research topic. In this study, microcrystalline CeMnO3 catalysts were prepared by a precipitant-concentration-induced strategy and evaluated for the catalytic oxidation of toluene/benzene. The effect of crystal size on catalytic performance was confirmed by XRD, TEM, N2 adsorption-desorption, XPS, Raman, H2-TPR, and TPSR. The CeMnO3 catalyst with more Mn3+-Ov-Ce4+ active sites exhibited enhanced VOCs catalytic oxidation performance, lowest active energy, and highest turnover frequency, which was attributed to its larger surface area, lower crystal size, higher low-temperature reducibility, and presence of more oxygen defects. In-situ FTIR results suggested more oxygen vacancies can profoundly promote the conversion of benzoate to maleate species, the rate-determining step of toluene oxidation. The work provides a convenient and efficient strategy to prepare single-metal or multi-metal oxide catalysts with smaller crystal sizes for VOC oxidation or other oxidation reactions.

Mn3O4/CuOx heterostructure for nitrate electroreduction to ammonia.

Here, we designed a Mn3O4/CuOx heterostructure supported on copper foil (CF) for electrocatalytic nitrate reduction to ammonia. The selectivity and Faraday efficiency of ammonia were 96.79% and 86.55%, respectively. Multiple characterizations revealed that Mn3O4/CuOx/CF showed faster charge transfer and created more electron-deficient Mn sites, electron-rich Cu sites and large numbers of oxygen vacancies, which were conducive to improving the catalytic activity. This work may open an avenue for the construction of heterostructures as an electrocatalyst for the reduction of nitrate to ammonia.

Understanding the Principles and Applications of Dual Z-Scheme Heterojunctions: How Far Can We Go?

In the past seven years, dual Z-scheme heterojunctions evolved as favorable approaches for enhanced charge carrier separation through direct or indirect charge transfer transportation mechanisms. The dynamics of the charge transfer is the major strategy for understanding their photoactivity and stability through the formation of distinctive redox centers. The understanding of currently recognized principles for successful fabrication and classification in different energy and pollution remediation strategies is discussed, and a universal charge transfer-type-based classification of dual Z-schemes that can be adopted for Z-scheme and S-scheme heterojunctions is proposed. Methods used for determining the charge transfer as proof of dual Z-scheme existence are outlined. Most importantly, a new macroscopic N-scheme and a triple Z-scheme that can also be adopted as triple S-scheme heterostructures composed of four semiconductors are proposed for generating both oxidatively and reductively empowered systems. The proposed systems are expected to possess properties that enable them to harvest solar light to drive important chemical reactions for different applications.

In Situ Generation of Fouling Resistant Ag/Pd Modified PES Membranes for Treatment of Pharmaceutical Wastewater.

In this study, Ag and Pd bimetallic nanoparticles were generated in situ in polyethersulfone (PES) dope solutions, and membranes were fabricated through a phase inversion method. The membranes were characterized for various physical and chemical properties using techniques such as FTIR, SEM, AFM, TEM, EDS, and contact angle measurements. The membranes were then evaluated for their efficiency in rejecting EOCs and resistance to protein fouling. TEM micrographs showed uniform distribution of Ag/Pd nanoparticles within the PES matrix, while SEM images showed uniform, fingerlike structures that were not affected by the presence of embedded nanoparticles. The presence of Ag/Pd nanoparticles resulted in rougher membranes. There was an increase in membrane hydrophilicity with increasing nanoparticles loading, which resulted in improved pure water permeability (37−135 Lm2h−1bar−1). The membranes exhibited poor salt rejection (<15%), making them less susceptible to flux decline due to concentration polarization. With a mean pore radius of 2.39−4.70 nm, the membranes effectively removed carbamazepine, caffeine, sulfamethoxazole, ibuprofen, and naproxen (up to 40%), with size exclusion being the major removal mechanism. Modifying the membranes with Ag/Pd nanoparticles improved their antifouling properties, making them a promising innovation for the treatment of pharmaceutical wastewater.

Toxicity assessment of TiO2-conjugated Carbon-based nanohybrid material on a freshwater bioindicator cladoceran, Daphnia magna.

The application of nanocomposite materials fabricated from titanium dioxide nanoparticles (TiO2 NPs) and different carbon (C) allotropes have gained popularity in water treatment applications due to their synergistic properties. Studies to date have focused on simple forms of nanomaterials (NMs), however, with the technology development, there is a dramatic increase in production and application of these complex NMs which could result in toxicological impacts on organisms when released into aquatic environments. This raises serious concerns about their safety and the need to ascertain their potential adverse effects on aquatic organisms. While conjugated TiO2 NPs/carbon-based nanohybrids (TiO2/C-NHs) may exhibit enhanced photocatalytic activity, there is no research in the scientific community regarding their toxicological effects on D. magna, which are indicators of freshwater pollution. In this study, two under-represented TiO2/C-NHs (i.e., TiO2- conjugated carbon nanofiber (CNF), and TiO2-conjugated multi-walled carbon nanotube (CNT)) were investigated for their toxic effects on D. magna, through a series of acute toxicity tests with a set of sublethal biochemical biomarkers of oxidative stress. The lethal toxicity and oxidative stress formation of TiO2/C-NHs over 48 h revealed a concentration-dependant increase in D. magna mortality. The primary mechanism identified was the generation of ROS, which was in line with toxicity results. Light microscopy and CytoViva® images visualized D. magna interaction with the NPs, which accumulated and appeared as dark materials in the lines of the gut tract. The collective results indicate that TiO2/C-NHs have the potential to cause an effect on freshwater organisms when released into the environment. However, the relevance of TiO2/C-NHs effects needs further chronic toxicity studies since they show promise to be used in nano-bioremediation materials to treat wastewaters.

Toxicity evaluation of TiO2/MWCNT-CNF hybrid nanocomposites with enhanced photocatalytic activity toward freshwater microalgae: Pseudokirchneriella subcapitata.

A wide range of semiconductor-assisted photocatalytic nanomaterials (NMs) are currently being considered and investigated as potential photocatalysts in water treatment. The applications of nanocomposites composed of nano-structured titania (nano-TiO2) and multi-walled carbon nanotubes (MWCNTs) nanocomposites is growing markedly on account of enhanced photocatalytic efficiency. However, concurrent with the increasing production and application comes a serious concern of these emerging nanosystems about their potential risks in aquatic systems, and thereby potentially threatening aquatic organisms via toxic mechanisms that are, at present, poorly understood. In the present study, the lethal toxic effect and oxidative stress induced by TiO2/MWCNT-CNF nanocomposite in freshwater Pseudokirchneriella subcapitata were assessed. The growth inhibition and sublethal oxidative stress produced by the nanocomposites were evaluated on green microalgae P. subcapitata after 3 days of exposure at 24 h intervals. Moreover, the nanocomposites were physicochemically characterized using a combination of analytical techniques (XRD, SEM/EDS, HRTEM, TGA, UV-Visible spectroscopy). Evaluation of the hybrid for the photocatalytic degradation of Acid Violet 7 dye indicated an enhanced dye removal performance for TiO2/MWCNT-CNF (96.2%) compared to TiO2 (75.2%) after 2 h of visible light irradiation. While the nanocomposite showed good potential for the degradation of the azo dye, overall, the findings herein indicated that acute exposure of P. subcapitata to various concentrations of TiO2/MWCNT-CNF nanocomposite may cause algal growth inhibition including undesirable sublethal oxidative stress effects. The findings of this study contribute to a better understanding of the potential hazards of the developing nanocomposites materials towards the nano-bioremediation materials to treat wastewaters.

Cobalt oxide/copper bismuth oxide/samarium vanadate (Co3O4/CuBi2O4/SmVO4) dual Z-scheme heterostructured photocatalyst with high charge-transfer efficiency: Enhanced carbamazepine degradation under visible light irradiation.

Herein, a dual Z-scheme heterojunction photocatalyst consisting of Co3O4, CuBi2O4, and SmVO4 for carbamazepine (CBZ) degradation was synthesised and characterised by XRD, FTIR, UV-Vis DRS, XPS, FE-SEM, and TEM. The reduction in electron-hole recombination was evaluated by PL, LSV, and EIS analysis. The heterojunction, Co3O4/CuBi2O4/SmVO4 (CCBSV) showed enhanced photocatalytic activity of 76.1% ± 3.81 CBZ degradation under visible light irradiation, ascribed to the improved interfacial contact, visible light capturing ability, and enhanced electron-hole separation and transportation through the formation of Z-scheme heterojunction. The formation of dual Z-scheme was confirmed by active radical experiments and XPS analysis that helped to prose the mechanism of degradation. The catalyst showed sustained stability after 4 cycles of reuse. Ultra-high-performance liquid chromatography-quadrupole time-of-flight mass spectrometry (UHPLC-QTOF-MS) was employed to identify the degradation by-products of CBZ, and a possible mechanistic degradation pathway was proposed. This study provided an insight into the development of efficient dual Z-scheme heterojunction photocatalyst for remediation of CBZ which can be extended to other organic pollutants.

Photo enhanced degradation of polyfluoroalkyl and perfluoroalkyl substances.

The increase in the presence of highly recalcitrant poly- and per- fluoroalkyl substances (PFAS) in the environment, plant tissues and animals continues to pose serious health concerns. Several treatment methods such as physical, biological and chemical processes have been explored to deal with these compounds. Current trends have shown that the destructive treatment processes, which offer degradation and mineralization of PFASs, are the most desirable process among researchers and policy makers. This article, therefore, reviews the degradation and defluorination processes, their efficiencies and the degradation mechanism of photon-based processes. It shows that high degradation and defluorination efficiency of PFASs could be achieved by photon driven processes such as photolysis, photochemical, photocatalysis and photoreduction. The efficiency of these processes is greatly influenced by the nature of light and the reactive radical generated in the system. The limitation of these processes, however, include the long reaction time required and the use of anoxic reaction conditions, which are not obtainable at ambient conditions.

Graphitic Carbon Nitride: A Highly Electroactive Nanomaterial for Environmental and Clinical Sensing.

Graphitic carbon nitride (g-C3N4) is a two-dimensional conjugated polymer that has attracted the interest of researchers and industrial communities owing to its outstanding analytical merits such as low-cost synthesis, high stability, unique electronic properties, catalytic ability, high quantum yield, nontoxicity, metal-free, low bandgap energy, and electron-rich properties. Notably, graphitic carbon nitride (g-C3N4) is the most stable allotrope of carbon nitrides. It has been explored in various analytical fields due to its excellent biocompatibility properties, including ease of surface functionalization and hydrogen-bonding. Graphitic carbon nitride (g-C3N4) acts as a nanomediator and serves as an immobilization layer to detect various biomolecules. Numerous reports have been presented in the literature on applying graphitic carbon nitride (g-C3N4) for the construction of electrochemical sensors and biosensors. Different electrochemical techniques such as cyclic voltammetry, electrochemiluminescence, electrochemical impedance spectroscopy, square wave anodic stripping voltammetry, and amperometry techniques have been extensively used for the detection of biologic molecules and heavy metals, with high sensitivity and good selectivity. For this reason, the leading drive of this review is to stress the importance of employing graphitic carbon nitride (g-C3N4) for the fabrication of electrochemical sensors and biosensors.

Preparation of carbon-coated brookite@anatase TiO2 heterophase junction nanocables with enhanced photocatalytic performance.

One-dimensional TiO2@C nanocables with a heterophase junction have been successfully prepared by coating brookite@anatase TiO2 with a thin layer of hydrothermal carbon (HTC). Compared with anatase TiO2, the biphase brookite@anatase structure can reduce the recombination rate of the excited electron/hole pairs of TiO2. The HTC coating not only enhances the adsorption capability of the TiO2 catalyst for organic pollutants but also facilitates photogenerated electron transfer to further increase its photocatalytic activity. Therefore, compared with anatase TiO2, brookite@anatase TiO2, and TiO2@C, the brookite@anatase TiO2@C shows the highest photocatalytic activity for the photodegradation of tetracycline (TC) under the irradiation of UV-visible light. Moreover, ˙O2 has been proved to be the predominant active species for the photodegradation of TC, and the photocatalytic mechanism of brookite@anatase TiO2@C nanocables has also been proposed.

Controlled Microwave-Assisted Synthesis of the 2D-BiOCl/2D-g-C3N4 Heterostructure for the Degradation of Amine-Based Pharmaceuticals under Solar Light Illumination.

Designing efficient 2D-bismuth oxychloride (BiOCl)/2D-g-C3N4 heterojunction photocatalysts by the microwave-assisted method was studied in this work using different amounts of BiOCl plates coupled with g-C3N4 nanosheets. The effects of coupling the 2D structure of g-C3N4 with the 2D structure of BiOCl were systematically examined by scanning electron microscopy (SEM), energy-dispersive X-ray spectroscopy, X-ray diffraction, photoluminescence (PL), lifetime decay measurement, surface charges of the samples at various pH conditions, and UV-vis diffuse reflectance spectroscopy (UV-vis DRS). The prepared photocatalysts were used for the degradation of amine-based pharmaceuticals, and nizatidine was used as a model pollutant to evaluate the photocatalytic activity. The UV-vis DRS and other optical properties indicated the major effect of coupling of BiOCl with g-C3N4 into a 2D/2D structure. The results showed a narrowing in the band gap energy of the composite form, whereas the PL and lifetime analysis showed greater inhibition of the electron-hole recombination process and slightly longer charge carrier lifetime. Accordingly, the BiOCl/g-C3N4 composite samples exhibited an enhancement in the photocatalytic performance, specifically for the 10% BiOCl/g-C3N4 sample. Moreover, the zeta potential of this sample at different pH values was evaluated to determine the isoelectric point of the synthesized composite material. Consequently, the pH was adjusted to match the isoelectric point of the complex materials, which further enhanced the activity. Further degradation of pharmaceuticals was studied under solar light irradiation, and 96% degradation was achieved within 30 min.

A Facile and Scalable Route to the Preparation of Catalytic Membranes with in Situ Synthesized Supramolecular Dendrimer Particle Hosts for Pt(0) Nanoparticles Using a Low-Generation PAMAM Dendrimer (G1-NH2) as Precursor.

Since the first reports of Cu dendrimer-encapsulated nanoparticles (DENs) published in 1998, the dendrimer-templating method has become the best and most versatile method for preparing ultrafine metallic and bimetallic nanoparticles (1-3 nm) with well-defined compositions, high catalytic activity, and tunable selectivity. However, DENs have remained for the most part model systems with limited prospects for scale up and integration into high-performance and reusable catalytic modules and systems for industrial-scale applications. Here, we describe a facile and scalable route to the preparation of catalytic polyvinylidene fluoride (PVDF) membranes with in situ synthesized supramolecular dendrimer particles (SDPs) that can serve as hosts and containers for Pt(0) nanoparticles (2-3 nm). These new catalytic membranes were prepared using a reactive encapsulation process similar to that utilized to prepare Pt DENs by addition of a reducing agent (sodium borohydride) to aqueous complexes of Pt(II) + G4-OH/G6-OH polyamidoamine (PAMAM) dendrimers. However, the SDPs (2.4 µm average diameter) of our new mixed matrix PVDF-PAMAM membranes were synthesized in the dope dispersion without purification prior to film casting using (i) a low-generation PAMAM dendrimer (G1-NH2) as particle precursor and (ii) epichlorohydrin, an inexpensive functional reagent, as cross-linker. In addition, the membrane PAMAM particles contain secondary amine groups (∼1.9 mequiv per gram of dry membrane), which are more basic and thus have higher Pt binding affinity than the tertiary amine groups of the G4-OH and G6-OH PAMAM dendrimers. Proof-of-concept experiments show that our new PVDF-PAMAM-G1-Pt/membranes can serve as highly active and reusable catalysts for the hydrogenation of alkenes and alkynes to the corresponding alkanes using (i) H2 at room temperature and a pressure of 1 bar and (ii) low catalyst loadings of ∼1.4-1.6 mg of Pt. Using cyclohexene as model substrate, we observed near quantitative conversion to cyclohexane (∼98%). The regeneration studies showed that our new Pt/membrane catalysts are stable and can be reused for five consecutive reaction cycles for a total duration of 120 h including 60 h of heating at 100 °C under vacuum for substrate, product, and solvent removal with no detectable loss of cyclohexene hydrogenation activity. The overall results of our study point to a promising, versatile, and scalable path for the integration of catalytic membranes with in situ synthesized SDP hosts for Pt(0) nanoparticles into high-throughput modules and systems for heterogeneous catalytic hydrogenations, an important class of reactions that are widely utilized in industry to produce pharmaceuticals, agrochemicals, and specialty chemicals.

Adsorption of cadmium, nickel and lead ions: equilibrium, kinetic and selectivity studies on modified clinoptilolites from the USA and RSA.

The performance of modified clinoptilolites (zeolites) from two different sources (South Africa and the USA) for the adsorption of Ni2+, Cd2+ and Pb2+ from synthetic industrial effluent contaminated with metal concentration levels at 50, 150 and 500 ppm was evaluated. The selectivity of the clinoptilolite for the adsorption of Ni2+, Cd2+ and Pb2+ was investigated with mixed feed solutions containing all three ions in equal concentrations and single-component concentrations containing only one of the ions. The homoionic forms of the clinoptilolite were made of Na+, K+ and Ca2+. Batch experiments were then conducted to measure the uptake of metals by the zeolites. The zeolites were characterised using SEM, XRD and BET. The South African clinoptilolite showed a higher surface area and pore volume (17.52m2/g and 0.047cm3/g respectively) than the USA zeolite (12.26m2/g and 0.028cm3/g respectively) for the Na+ homoionic form. According to the equilibrium studies, the selectivity sequence was found to be Pb2+ > Cd2+ > Ni2+, with good fits being obtained using Langmuir and Freundlich adsorption isotherms for low metal concentrations. Examples of equilibrium adsorption capacities for RSA and USA clinoptilolite modified with Na+ for Pb were 26.94 mg/g and 27.06 mg/g when RSA-Na+ and USA-Na+ were used respectively. The adsorption was found to depend on the homoionic form of the zeolite and to a lesser extent the source of the zeolite. The selectivity of a particular zeolite for a particular heavy metal can be altered by the homoionic form of the zeolite. Overall, the adsorption capacity of the USA clinoptilolite was higher than the adsorption capacity of the SA clinoptilolite, revealing the potential of clinoptilolite in metal-polluted industrial effluent treatment.

Facile Synthesis of Nitrogen Doped Graphene Oxide from Graphite Flakes and Powders: A Comparison of Their Surface Chemistry.

Nitrogen-doped graphene oxide (NGO) nanosheets were prepared via a facile one-pot modified Hummer's approach at low temperatures using graphite powder and flakes as starting materials in the presence of a nitrogen precursor. It was found that the morphology, structure, composition and surface chemistry of the NGO nanosheets depended on the nature of the graphite precursor used. GO nanosheets doped with nitrogen atoms exhibited a unique structure with few thin layers and wrinkled sheets, high porosity and structural defects. NGO sheets made from graphite powder (NGOp) exhibited excellent thermal stability and remarkably high surface area (up to 240.53 m2 ·g-1) compared to NGO sheets made from graphite flakes (NGOf) which degraded at low temperatures and had an average surface area of 24.70 m2 ·g-1. NGOf sheets had a size range of 850 to 2200 nm while NGOp sheets demonstrated obviously small sizes (460-1600 nm) even when exposed to different pH conditions. The NGO nanosheets exhibited negatively charged surfaces in a wide pH range (1 to 12) and were found to be stable above pH 6. In addition, graphite flakes were found to be more suitable for the production of NGO as they produced high N-doping levels (0.65 to 1.29 at.%) compared to graphite powders (0.30 to 0.35 at.%). This study further demonstrates that by adjusting the amount of N source in the host GO, one can tailor its thermal stability, surface morphology, surface chemistry and surface area.

Mixed Matrix PVDF Membranes With in Situ Synthesized PAMAM Dendrimer-Like Particles: A New Class of Sorbents for Cu(II) Recovery from Aqueous Solutions by Ultrafiltration.

Advances in industrial ecology, desalination, and resource recovery have established that industrial wastewater, seawater, and brines are important and largely untapped sources of critical metals and elements. A Grand Challenge in metal recovery from industrial wastewater is to design and synthesize high capacity, recyclable and robust chelating ligands with tunable metal ion selectivity that can be efficiently processed into low-energy separation materials and modules. In our efforts to develop high capacity chelating membranes for metal recovery from impaired water, we report a one-pot method for the preparation of a new family of mixed matrix polyvinylidene fluoride (PVDF) membranes with in situ synthesized poly(amidoamine) [PAMAM] particles. The key feature of our new membrane preparation method is the in situ synthesis of PAMAM dendrimer-like particles in the dope solutions prior to membrane casting using low-generation dendrimers (G0 and G1-NH2) with terminal primary amine groups as precursors and epichlorohydrin (ECH) as cross-linker. By using a combined thermally induced phase separation (TIPS) and nonsolvent induced phase separation (NIPS) casting process, we successfully prepared a new family of asymmetric PVDF ultrafiltration membranes with (i) neutral and hydrophilic surface layers of average pore diameters of 22-45 nm, (ii) high loadings (∼48 wt %) of dendrimer-like PAMAM particles with average diameters of ∼1.3-2.4 µm, and (iii) matrices with sponge-like microstructures characteristics of membranes with strong mechanical integrity. Preliminary experiments show that these new mixed matrix PVDF membranes can serve as high capacity sorbents for Cu(II) recovery from aqueous solutions by ultrafiltration.

Photocatalytic performance of nitrogen, osmium co-doped TiO2 for removal of eosin yellow in water under simulated solar radiation.

Nitrogen, osmium co-doped TiO2 photocatalysts were prepared by a modified sol-gel method using ammonia as the nitrogen source and osmium tetroxide as the source of osmium. The role of rutile phase OsO2 in enhancing the photocatalytic activity of rutile TiO2 towards the degradation of Eosin Yellow was investigated. The materials were characterised by various techniques that include FTIR, Raman, XRD, SEM, EDS, TEM, TGA and DRUV-Vis. The amorphous, oven dried sample was transformed to the anatase and then the rutile phase with increasing calcination temperature. DRUV-Vis analysis revealed a red shift in absorption with increasing calcination temperature, confirmed by a decrease in the band gap of the material. The photocatalytic activity of N, Os co-doped TiO2 was evaluated using eosin yellow degradation and activity increased with increase in calcination temperature under simulated solar irradiation. The rutile phase of the co-doped TiO2 was found to be more effective in degrading the dye (k(a) = 1.84 x 10(-2) min(-1)) compared to the anatase co-doped phase (k(a) = 9.90 x 10(-3) min(-1)). The enhanced photocatalytic activity was ascribed to the synergistic effects of rutile TiO2 and rutile OsO2 in the N, Os co-doped TiO2.

Stabilisation of silver and copper nanoparticles in a chemically modified chitosan matrix.

This work describes the stabilisation of silver and copper nanoparticles in chemically modified chitosan colloidal solution. Chitosan-N-2-methylidene-hydroxy-pyridine-6-methylidene hydroxy thiocarbohydrazide (CSPTH) was used as a stabilising and reducing agent for silver and copper nanoparticles. The modified chitosan derivatives and the synthesised nanoparticles were characterised by Fourier transform infrared (FT-IR) spectroscopy, Ultraviolet-visible (UV-Vis) spectroscopy and X-ray diffraction (XRD). Particle size, morphology and segregation of the nanoparticles were determined by transmission electron microscopy (TEM). The size of the nanoparticles was found to be less than 20 nm and 50 nm for silver and copper nanoparticles, respectively. These nanoparticles were stabilised in a chemically modified chitosan solution and their properties were studied using fluorescence spectroscopy, photoluminescence spectroscopy and surface-enhanced Raman scattering (SERS). The optical properties of silver nanoparticles in surface plasmon band (SPB) were enhanced at 407 nm compared to those of copper nanoparticles. Fluorescence (400 nm and 756 nm), photoluminescence (450 and 504 nm) and Raman scattering (1382 and 1581 cm(-1)) properties for the copper nanoparticles were superior to those of the silver nanoparticles.