Effective aqueous chromate treatment using triethanolamine anacardate coated magnetic nanoparticles.

Low-cost adsorbents derived from agricultural by-products incorporated magnetic nanoparticles (NPs) are promising for wastewater treatment. They are always preferred due to their great performance and easy separation. This study reports cobalt superparamagnetic (CoFe2O4) nanoparticles (NPs) incorporated with triethanolamine (TEA) based surfactants from cashew nut shell liquid, namely TEA-CoFe2O4, for the removal of chromium (VI) ions from aqueous solutions. To have detailed characteristics of the morphology and structural properties, scanning electron microscopy (SEM), X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FT-IR) and vibrating sample magnetometry (VSM) were employed. The fabricated TEA-CoFe2O4 particles exhibit soft and superparamagnetic properties, which make the nanoparticles easily recycled by using a magnet. Chromate adsorption on the TEA-CoFe2O4 nanomaterials reached an optimal efficiency of 84.3% at pH = 3 with the initial adsorbent dose of 10 g/L and chromium (VI) concentration of 40 mg/L. The TEA-CoFe2O4 nanoparticles can maintain the effective adsorption of chromium (VI) ion (by 29% of efficiency loss) and retain the magnetic separation using a magnet up to three cycles of the regeneration, which promise a high potential of this low-cost adsorbent for long-term treatment of heavy metal ions from polluted waters.

Halides and oxyhalides-based photocatalysts for abatement of organic water contaminants - An overview.

Recently, halides (silver halides, AgX; perosvkite halides, ABX3) and oxyhalides (bismuth oxyhalides, BiOX) based nanomaterials are noticeable photocatalysts in the degradation of organic water pollutants. Therefore, we review the recent reports to explore improvement strategies adopted in AgX, ABX3 and BiOX (X = Cl, Br and I)-based photocatalysts in water pollution remediation. Herein, the photocatalytic degradation performances of each type of these photocatalysts were discussed. Strategies such as tailoring the morphology, crystallographic facet exposure, surface area, band structure, and creation of surface defects to improve photocatalytic activities of pure halides and BiOCl photocatalysts are emphasized. Other strategies like metal ion and/or non-metal doping and construction of composites, adopted in these photocatalysts were also reviewed. Furthermore, the way of production of active radicals by these photocatalysts under ultraviolet/visible light source is highlighted. The deciding factors such as structure of pollutant, light sources and other parameters on the photocatalytic performances of these materials were also explored. Based on this literature survey, the need of further research on AgX, ABX3 and BiOX-based photocatalysts were suggested. This review might be beneficial for researchers who are working in halides and oxyhalides-based photocatalysis for water treatment.

Recent progress in green and biopolymer based photocatalysts for the abatement of aquatic pollutants.

Enormous research studies on the abatement of anthropogenic aquatic pollutants including organic dyes, pesticides, cosmetics, antibiotics and inorganic species by using varieties of semiconductor photocatalysts have been reported in recent decades. Besides, many of these photocatalysts suffer in real applications owing to their high production cost and low stability. In many cases, the photocatalysts themselves are being considered as secondary pollutants. To eliminate these drawbacks, the green synthesized photocatalysts and the use of biopolymers as photocatalyst supports are considered in recent years. In this context, recent developments in green synthesized metals, metal oxides, other metal compounds, and carbon based photocatalysts in water purification are critically reviewed. Furthermore, the pivotal role of biopolymers including chitin, chitosan, cellulose, natural gum, hydroxyapatite, alginate in photocatalytic removal of aquatic pollutants is comprehensively reviewed. The presence of functional groups, electron trapping ability, biocompatibility, natural occurrence, and low production cost are the major reasons for using biopolymers in photocatalysis. Finally, the summary and conclusion are presented along with existing challenges in this research area.

Solution/Ammonolysis Syntheses of Unsupported and Silica-Supported Copper(I) Nitride Nanostructures from Oxidic Precursors.

Herein we describe an alternative strategy to achieve the preparation of nanoscale Cu3N. Copper(II) oxide/hydroxide nanopowder precursors were successfully fabricated by solution methods. Ammonolysis of the oxidic precursors can be achieved essentially pseudomorphically to produce either unsupported or supported nanoparticles of the nitride. Hence, Cu3N particles with diverse morphologies were synthesized from oxygen-containing precursors in two-step processes combining solvothermal and solid-gas ammonolysis stages. The single-phase hydroxochloride precursor, Cu2(OH)3Cl was prepared by solution-state synthesis from CuCl2·2H2O and urea, crystallising with the atacamite structure. Alternative precursors, CuO and Cu(OH)2, were obtained after subsequent treatment of Cu2(OH)3Cl with NaOH solution. Cu3N, in the form of micro- and nanorods, was the sole product formed from ammonolysis using either CuO or Cu(OH)2. Conversely, the ammonolysis of dicopper trihydroxide chloride resulted in two-phase mixtures of Cu3N and the monoamine, Cu(NH3)Cl under similar experimental conditions. Importantly, this pathway is applicable to afford composite materials by incorporating substrates or matrices that are resistant to ammoniation at relatively low temperatures (ca. 300 °C). We present preliminary evidence that Cu3N/SiO2 nanocomposites (up to ca. 5 wt.% Cu3N supported on SiO2) could be prepared from CuCl2·2H2O and urea starting materials following similar reaction steps. Evidence suggests that in this case Cu3N nanoparticles are confined within the porous SiO2 matrix.

Highly Sustainable Zinc Anodes for a Rechargeable Hybrid Aqueous Battery.

The synthesis of novel zinc electrodes has been successfully implemented by using the electroplating method with the aid of inorganic additives in the electroplating solution. The selected inorganic additives are indium sulfate, tin oxide, and boric acid. From X-ray diffraction results, these synthesized zinc electrodes prefer (002) and/or (103) crystallographic orientations, representing basal morphology and high resistance to dendrite growth. The corrosion rates of these electroplated zinc samples decrease as much as 11 times smaller than the corrosion rate on zinc foil when the zinc materials are in contact with the aqueous electrolyte of a rechargeable hybrid aqueous battery (ReHAB). The ReHABs employing these anodes exhibit up to a threefold decrease in float charge current density after a seven-day constant-voltage charging at 2.1 V versus Zn2+ /Zn. Furthermore, the capacity retention is up to 15 % higher than the performance of battery containing commercial Zn after 1000 cycles of charge-discharge. The significant advancements are attributed to the careful preparation of the anode, which contains appropriate crystallographic orientation and morphology.

Effect of Imidazole on the Electrochemistry of Zinc Porphyrins: An Electrochemical and Computational Study.

In this study, the electrochemical behavior of zinc meso-substituted porphyrins in the presence of imidazole is examined by using both cyclic voltammetry (CV) and density functional theory (DFT) methods. The results show that the first half-wave oxidation potentials (1st E1/2) of zinc porphyrins complexed with imidazole all move to the negative side, while the second ones (2nd E1/2) move to the positive side, resulting in larger half-wave oxidation potential splittings of the two oxidation states (ΔE = second E1/2 - first E1/2) comparing with the zinc porphyrins. By employing DFT calculations, we have found that both sterically controlled inter π-conjugation between porphyrin rings and meso-substituted phenyl groups and deformation of porphyrin rings do play important roles in contributing to the half-wave oxidation potentials. Imidazole exhibits strong effects on the deformation of porphyrin rings which is dominant in determining the first E1/2 while the inter π-conjugation between porphyrin rings and meso-substituted phenyl groups mainly contributes to the second E1/2. Without imidazole, the inter π-conjugation between porphyrin rings and meso-substituted phenyl groups is the only important criterion which effects both first E1/2 and second E1/2 of zinc porphyrins.

Electrochemical Behavior of meso-Substituted Porphyrins: The Role of Cation Radicals to the Half-Wave Oxidation Potential Splitting.

In this study, the electrochemical behavior of free base and zinc meso-substituted porphyrins is examined by cyclic voltammetry (CV) and density functional theory (DFT). The results show that the half-wave oxidation potential splitting of the two oxidation states (ΔE= second E1/2 - first E1/2) of tetraphenylporphyrin (H2TPP) and its zinc complex (ZnTPP) are higher than those of porphyrins and their zinc complexes with meso-substituted five-membered heterocylic rings. The ΔE values follow the trend of TPP > T(3'-thienyl)P > T(3'-furyl)P > T(2'-thienyl)P for both meso-porphyrins and their respective zinc complexes. By employing DFT calculations, we have found that the trend of ΔE values is consistent with that of highest spin density (HSD) distribution and HOMO-LUMO energy gaps of cationic radicals as well as the π-conjugation between central porphyrin and meso-substituted rings. Also, they exhibit the better resonance between the porphyrin ring with meso-substituted rings as moving from porphyrins and their zinc complexes with phenyl rings to five-membered heterocyclic rings. A good agreement between calculated and experimental results indicates that cationic radicals, especially their spin density distribution, do play an important role in half-wave oxidation potential splitting of meso-porphyrins and their zinc complexes.

The effect of sulfur loading on the electrochemical performance of a sulfur-polymer composite cathode coated on aluminium foil.

A scaling-up investigation of a sulfur-polymer cathode for rechargeable lithium-sulfur batteries is reported. The proposed procedure uses a low cost aluminium current collector and is suitable for mass production of a composite cathode, with sulfur loading levels of up to 5.9 mg cm(-2), and good electrochemical performance.

Well-dispersed Ni3Fe nanoparticles with a N-doped porous carbon shell for highly efficient rechargeable Zn-air batteries.

NiFe-based nanoparticles attached to heteroatom-doped carbon are found to act as tremendously efficient oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) electrocatalysts. Nevertheless, it is extremely challenging to control the particle size and avoid aggregation. Herein, nitrogen-doped carbon encapsulated Ni3Fe nanoparticles (Ni3Fe@NC) are prepared by two-stage pyrolysis with a low rate based on the in situ structural evolution of FeNi-PBAs. The strategy results in uniform Ni3Fe nanoparticles anchoring within the carbon shell and thus facilitating interfacial interaction. Benefiting from the enhanced synergism between Ni3Fe particles and NC layers, Ni3Fe@NC-600 demonstrates the best catalytic activity and durability, not only with almost the same onset potential (1.01 V) as commercial Pt/C for the ORR but also satisfactory OER performance with a low overpotential of 0.29 V at 10 mA cm-2 in 0.1 M KOH. Moreover, the Zn-air battery assembled using the Ni3Fe@NC-600 cathode exhibits superior performance to commercial Pt/C + RuO2. The simple and scalable method of this work provides insight into the fabrication of high-performance and cost-effective bifunctional oxygen electrocatalysts.

Photobiological effects of converting biomass into hydrogen - Challenges and prospects.

In comparison to other methods of producing hydrogen, the production of biohydrogen is significantly less harmful to the surrounding ecosystem when it was produced from the biological origin such as microalgae. It could take the place of conventional fossil fuels while avoiding the emission of greenhouse gases. The substrates such as food, agricultural waste, and industrial waste can be readily utilized after the necessary pretreatment, led to an increase in the yield of hydrogen. Improving the production of biofuels at each stage can have a significant impact on the final results, making this method a potentially useful instrument. As a consequence of this, numerous approaches to pretreat the algal biomass, numerous types of enzymes and catalyst that play a crucial role for hydrogen production, the variables that influence the production of hydrogen, and the potential applications of genetic engineering have all been comprehensively covered in this study.

Effects of Various Valence Ions on an Aqueous Rechargeable Zn//Polyaniline-coated ZnMn2 O4 Battery.

Zinc corrosion and dendrite formation are the main issues which impede the performance of aqueous zinc ion batteries (ZIBs) after certain times. In this work, we systematically investigated the effects of three different valence ions (e. g., Na+ , Mg2+ , Al3+ ) as electrolyte additives on the suppression of zinc corrosion and the inhibition of dendrite growth. By combining experiments and theoretical calculations, it has been found that the existence of Na+ ions effectively suppressing the zinc dendrite growth because Na+ possessess high adsorption energy approximately -0.39 eV. Moreover, Na+ ions could lengthen the zinc dendrite formation duration up to 500 h. On the other hand, the PANI/ZMO cathode materials showed the small band gap approximately 0.097 eV, signifying that the PANI/ZMO possessed the semiconductor characteristics. Furthermore, an assembled Zn//PANI/ZMO/GNP full battery using Na+ ions as electrolyte additive displayed capacity retention of 90.2 % after 500 cycles at 0.2 A g-1 , whereas the capacity retention of the control battery using pure ZnSO4 electrolyte was only 58.2 %. This work could provide a reference for the selection of electrolyte additives in future batteries.

Transition metal hydrazide-based hydrogen-storage materials: the first atoms-in-molecules analysis of the Kubas interaction.

Molecular models of the M-H(2) binding sites of experimentally characterised amorphous vanadium hydrazide gels are studied computationally using gradient corrected density functional theory, to probe the coordination number of the vanadium in the material and the nature of the interaction between the metal and the H(2) molecules. The H(2) is found to bind to the vanadium through the Kubas interaction, and the first quantum theory of atoms-in-molecules analysis of this type of interaction is reported. Strong correlation is observed between the electron density at the H-H bond critical point and the M-H(2) interaction energy. Four coordinate models give the best reproduction of the experimental data, suggesting that the experimental sites are four coordinate. The V-H(2) interaction is shown to be greater when the non-hydrazine based ligand, THF, of the experimental system is altered to a poorer π-acceptor ligand. Upon altering the metal to Ti or Cr the M-H(2) interaction energy changes little but the number of H(2) which may be bound decreases from four (Ti) to two (Cr). It is proposed that changing the metal from V to Ti may increase the hydrogen storage capacity of the experimental system. A 9.9 wt% maximum storage capacity at the ideal binding enthalpy for room temperature performance is predicted when the Ti metal is combined with a coordination sphere containing 2 hydride ligands.

A review on MXene and its nanocomposites for the detection of toxic inorganic gases.

In the search of the viable candidate for the sensing of pollutant gases, two-dimensional (2D) material transition metal carbides (MXenes) have attracted immense attention due to their outstanding physical and chemical properties for sensing purposes. The formation of unique 2D layered structure with high conductivity, large mechanical strength, and high adsorption properties furnish their strong interactions with gaseous molecules, which holds a promising place for developing ideal gas sensing devices. This review looks at recent achievements in diversified MXenes, with a focus gaining on in-depth understanding of MXene-based materials in room temperature inorganic gas sensors through both theoretical and experimental studies. In the first part of the review, the properties and advantages of sensing material (MXene) in comparison with other 2D materials are discussed. In the second part, the unique advantages of chemiresistive based sensors and the demerits of other detection methods are summarized in detail. This section is followed by the unique structural design of MXene bases materials for improving the sensing performance towards detection of inorganic gases. The interaction between MXene and the adsorbed gases on its surface is discussed, with a possible sensing mechanism. Finally, an overview of the current progress and opportunities for the demand of MXene is emphasized and perspectives for future improvement of the design of MXene in gas sensors are highlighted. Therefore, this review highlights the opportunities and the advancement in 2D material-based gas sensors which could provide a new avenue for rapid detection of toxic gases in the environment.

The role of MOF based nanocomposites in the detection of phenolic compounds for environmental remediation- A review.

Phenolic compounds would be the emerging pollutant by 2050, because of their wide spread applicability in daily life and therefore the adoption of suitable detection methods in which identification and separation of isomers is highly desirable. Owing to the fascinating features, Metal-organic framework (MOF), a class of reticular materials holds a large surface area with tunable shape and adjustable porosity will provide strong interaction with analytes through abundant functional groups resulting in high selectivity towards electrochemical determination of phenolic isomers. Nevertheless, the sensing performance can still be further improved by building MOF network (intrinsic resistance) with functional (conducting) materials, resulting in MOF based nanocomposite. Herein, this review provides the summary of MOF based nanocomposites for electrochemical sensing of phenolic compounds developed from 2015. In this review, we discussed the demerits of pristine MOF as electrode materials, and the requirement of new class of MOF with functional materials such as nanomaterials, carbon nanotubes, graphene and MXene. The history and evolution of MOF nanocomposite-based materials are discussed and also featured the impressive physical and chemical properties. Besides this review discusses the factors influencing the conducting pathway and mass transport of MOF based nanocomposite for enhanced sensing performance of phenolic compounds with suitable mechanistic illustrations. Finally, the major challenges governing the determination of phenolic compounds and the future advancements required for the development of MOF based electrodes for various applications are highlighted.

Recent trends and advancements in nanoporous membranes for water purification.

When it comes to electrocatalysis, the creation of nanodevices, the research of energy and the environment, and diagnostics, nanoporous materials are an asset. Nanoporous membranes, which can be used to filter water, have recently been the subject of new research and are summarized in this review. These membranes are used to remove salts and metallic ions from the water following an analysis of several nanoporous membrane types and production procedures. Demonstrations and discussions of these membrane systems are then conducted. Nanoporous membranes can be used to filter water, according to the conclusions of this study, which will help readers better grasp how they work. As a result, novel water purification nanoporous compounds that are easy to manufacture, inexpensive, and effective will be developed. Merits and demerits of nanoporous membrane for water treatment and its advancements in purification were discussed.

Recent developments on graphene and its derivatives based electrochemical sensors for determinations of food contaminants.

The sensing of food contaminants is essential to prevent their adverse health effects on the consumers. Electrochemical sensors are promising in the determination of electroactive analytes including food pollutants, biomolecules etc. Graphene nanomaterials offer many benefits as electrode material in a sensing device. To further improve the analytical performance, doped graphene or derivatives of graphene such as reduced graphene oxide and their nanocomposites were explored as electrode materials. Herein, the advancements in graphene and its derivatives-based electrochemical sensors for analysis of food pollutants were summarized. Determinations of both organic (food colourants, pesticides, drugs, etc.) and inorganic pollutants (metal cations and anions) were considered. The influencing factors including nature of electrode materials and food pollutants, pH, electroactive surface area etc., on the sensing performances of modified electrodes were highlighted. The results of pollutant detection in food samples by the graphene-based electrode have also been outlined. Lastly, conclusions and current challenges in effective real sample detection were presented.

Hybrid metal organic frameworks as an Exotic material for the photocatalytic degradation of pollutants present in wastewater: A review.

In this world, water is considered as the Elixir for all living creatures. Human life rolls with water, and every activity depends upon water. Worldwide water resources are being contaminated due to the elevation in the population count, industrialization and urbanization. Ejection of chemicals by industries and domestic sewages remains the major reason in the destruction of natural water resources. Contaminated water with harmful microbes, chemical dyes, pesticides, and carcinogens are the root cause of many diseases and deaths of living species. In this scenario, researchers engaged in producing ultra components to remove the contaminants. Metal organic frameworks (MOF) are the desired combination of organic and inorganic materials to achieve the required target. MOFs possess unique characteristics like tunable internal structure, porosity, crystallinity and high surface area which enable them for energy and environmental application. For the past years, MOFs are concentrated more as a photocatalyst in the treatment of polluted water. These research studies discuss the improvement of photocatalytic performance of MOF by the incorporation of metals, metal coupled with nanoparticles like polymers, graphene, etc., into it to achieve the enhanced photocatalytic activity by scavenging entire chemicals and harmful microbes to retain the quality of water. The target of this review article is to focus on the state of the art research work on MOFs in photocatalytic water treatment technique.

Generation of novel n-p-n (CeO2-PPy-ZnO) heterojunction for photocatalytic degradation of micro-organic pollutants.

Recently, hetero junction materials (p-n-p and n-p-n) have been developed for uplifting the visible light activity to destroy the harmful pollutants in wastewater. This manuscript presents a vivid description of novel n-p-n junction materials namely CeO2-PPy-ZnO. This novel n-p-n junction was applied as the photocatalyst in drifting the mobility of charge carriers and hence obtaining the better photocatalytic activity when compared with p-n and pure system. Such catalyst's syntheses were successful via the copolymerization method. The structural, morphological and optical characterization techniques were applied to identify the physio-chemical properties of the prepared materials. Additionally, the superior performance of this n-p-n nanostructured material was demonstrated in the destruction of micro organic (chlorophenol) toxic wastes under visible light. The accomplished ability of the prepared catalysts (up to 92% degradation of chlorophenol after 180 min of irradiation) and their profound degradation mechanism was explained in detail.

Investigation of mechanism of heavy metals (Cr6+, Pb2+& Zn2+) adsorption from aqueous medium using rice husk ash: Kinetic and thermodynamic approach.

In this work, we examined the possibility on the application of rice husk as biosorbent for the elimination of heavy metal ions (chromium, lead, and zinc) existing in the aqueous solutions. The biosorbent was prepared from rice husk powder and modified with 0.1 N of HCl for creating the functional groups and increase specific surface area. The FT-IR spectra, SEM& EDX studies of rice hulls powder were examined for the pristine adsorbent and after the adsorption of heavy metal ions. The batch adsorption technique was adopted for this work and adsorption parameters were optimized. The maximum efficiency of adsorption is obtained at 6.0 pH, 1 h of contact duration, the rice husk dosage is 2.5 g/L, and temperature of 30°C for 25 mg/L of Cr, Pb & Zn metal ion solutions. The Cr, Pb & Zn metal ions are removed up to 87.12 %, 88.63 % & 99.28 %, respectively, using the rice husk powder. The adsorption process follows the Temkin & D-R isotherm model. Elovich model was fitted against the kinetic data of metal ion adsorption. Based on the experimental observations, the rice husk powder can be considered as a low cost adsorbent for heavy metal ion removal from the industrial effluent.

Recent development of organic-inorganic hybrid photocatalysts for biomass conversion into hydrogen production.

Over the last few years, photocatalysis using solar radiation has been explored extensively to investigate the possibilities of producing fuels. The production and systematic usage of solar fuels can reduce the use of fossil-based fuels, which are currently the primary source for the energy. It is time for us to exploit renewable sources for our energy needs to progress towards a low-carbon society. This can be achieved by utilizing green hydrogen as the future energy source. Solar light-assisted hydrogen evolution through photocatalytic water splitting is one of the most advanced approaches, but it is a non-spontaneous chemical process and restricted by a kinetically demanding oxidation evolution reaction. Sunlight is one of the essential sources for the photoreforming (PR) of biomass waste into solar fuels, or/and lucrative fine chemicals. Hydrogen production through photoreforming of biomass can be considered energy neutral as it requires only low energy to overcome the activation barrier and an alternate method for the water splitting reaction. Towards the perspective of sustainability and zero emission norms, hydrogen production from biomass-derived feedstocks is an affordable and efficient process. Widely used photocatalyst materials, such as metal oxides, sulphides and polymeric semiconductors, still possess challenges in terms of their performance and stability. Recently, a new class of materials has emerged as organic-inorganic hybrid (OIH) photocatalysts, which have the benefits of both components, with peculiar properties and outstanding energy conversion capability. This work examines the most recent progress in the photoreforming of biomass and its derivatives using OIHs as excellent catalysts for hydrogen evolution. The fundamental aspects of the PR mechanism and different methods of hydrogen production from biomass are discussed. Additionally, an interaction between both composite materials at the atomic level has been discussed in detail in the recent literature. Finally, the opportunities and future perspective for the synthesis and development of OIH catalysts are discussed briefly with regards to biomass photo-reforming.