Nanomaterial grafted polymorphous activated carbon cloth surface for antibacterial, capacitive deionization and oil spill cleaning applications.

This work reports the development of multifunctional or polymorphous surfaces using zinc oxide (ZnO) nanorods, silica (SiO2), and fluoropolymer functionalization in a sequential process. Firstly, zinc oxide nanorods were grown on activated carbon cloth (ACC) using a simple low-temperature synthesis process. ZnO nanorods-coated ACC substrate was applied to investigate the antimicrobial properties, and the results showed inhibition of 50% for Escherichia coli (E.coli) and 55% for Bacillus subtilis (B.subtilis) over 48 h of incubation time. Subsequent in-situ modification of silica nanoparticles like layer on ZnO nanorods-coated ACC surface was developed and used as an electrode for brackish water desalination in a capacitive deionization system. ZnO-SiO2 modified ACC surface enhanced the desalination efficiency by 1.6 times, the salt removal rate (SRR) by threefold, and the durability (fouling prevention) for long-term usage compared to pristine ACC. Further modification of the ZnO-SiO2-ACC surface using fluoropolymer rendered the surface superhydrophobic and oleophilic. Vegetable (1.4 g/g) and crude oil (1.6 g/g) adsorption capacities were achieved for modified surface which was 70% enhancement compared with pristine ACC. The dynamic oil spill adsorption test exhibited the complete removal of oil spills on water surfaces within a few seconds, suggesting a potential application in oil spill cleaning.

Development of portable sensor for the detection of bacteria: effect of gold nanoparticle size, effective surface area, and interparticle spacing upon sensing interface.

In this study, systematic development of a portable sensor for the rapid detection of Escherichia coli (E. coli) and Exiguobacterium aurantiacum (E. aurantiacum) was reported. A conductive glass was utilized as a substrate and developed the electrode patterns on it. Trisodium citrate (TSC) and chitosan-stabilized gold nanoparticles (AuNPs) (CHI-AuNP-TSC) and chitosan-stabilized AuNPs (CHI-AuNP) were synthesized and utilized as a sensing interface. The morphology, crystallinity, optical properties, chemical structures, and surface properties of immobilized AuNPs on the sensing electrodes were investigated. The sensing performance of the fabricated sensor was evaluated by using an electrochemical method to observe the current changes in cyclic voltammetric responses. The CHI-AuNP-TSC electrode has higher sensitivity toward E. coli than CHI-AuNP with a limit of detection (LOD) of 1.07 CFU/mL. TSC in the AuNPs synthesis process played a vital role in the particle size, the interparticle spacing, the sensor's effective surface area, and the presence of CHI around AuNPs, thus enhancing the sensing performance. Moreover, post-analysis of the fabricated sensor surface exhibited the sensor stability and the interaction between bacteria and the sensor surface. The sensing results showed a promising potential for rapid detection using a portable sensor for various water and food-borne pathogenic diseases.

Autopsy of Used Reverse Osmosis Membranes from the Largest Seawater Desalination Plant in Oman.

The Barka desalination plant, commissioned in 2018, is the largest desalination plant in Oman. It has a capacity of 281 MLD with a reverse osmosis (RO) first-pass recovery rate of 46%. As part of the standard operator practice, a membrane autopsy was conducted to determine the cause of reductions in membrane performance. This study investigated fouled membranes (model No. SW30HRLE-440) from two different locations in the membrane rack. Various analytical methods were used to conduct the membrane autopsy. Field-emission scanning electron microscopy/energy-dispersive X-ray (FESEM/EDS) analyses of membrane samples showed major components of inorganic foulants. Moreover, black and salt-like crystals deposited on the membrane surface revealed significant carbon (C) components and oxygen (O), with a small amount of magnesium (Mg), chloride (Cl), sodium (Na), aluminium (Al), and calcium (Ca), respectively. A Fourier transform infrared (FTIR) analysis revealed the presence of long-chain hydrocarbons, carboxylic acids/esters, carbohydrates/polysaccharides, and inorganic foulants. Thermogravimetric analyses (TGA) of the membranes showed a high initial weight loss due to organic and inorganic fouling. X-ray photoelectron (XPS) analyses further confirmed the presence of inorganic and organic foulants on the membrane surfaces. Bacteria identification results showed the presence of Bacillus cereus and Bacillus marisflavi. This paper offers a detailed analysis of the foulants present on the reverse osmosis membrane surface and sub-surface before and after a cleaning process.

Effects of crystallization temperature on the characteristics of sugar crystals in date fruit syrup as measured by differential scanning calorimetry (DSC), polarized microscopy (PLM), and X-ray diffraction (XRD).

Characteristics of sugar crystals are important for developing set-syrup due to their contribution to the desired mouth feel when consumed. Two types of set-syrup (i.e. seeds with and without) were developed by storing the syrup at -20, 4 and 15 °C. The melting temperatures (onset and peak), and enthalpy of set-syrup without seeds (SN) were 30.2 °C, 74.6 °C and 42.2 kJ/kg respectively. In the case of SN, enthalpy decreased with the decrease of crystallization temperature (P < 0.05), while there was insignificant change in the case of set-syrup with seeds (SW) (P > 0.05). Polarized Light Microscopy (PLM) images showed that finer crystals were formed in the cases of set-syrups (i.e. SN and SW) as the storage temperature was decreased. X-ray diffraction (XRD) analysis showed the formation of different polymorphic sugar crystals. Crystallization temperatures at 4 and -20 °C can be used to produce finer crystals with varied polymorphic characteristics.

ZnO nanorod-chitosan composite coatings with enhanced antifouling properties.

The current study describes the fabrication of chitosan­zinc oxide nanorods composite (CHT/ZnO) on fiberglass panels (support substrate). ZnO nanorods (NRs) with size ranging from 20 to 100 nm and some microrods with an approximate size of 0.5-1 µm were grown on fiberglass panels. CHT 1%/ZnO composite had ZnO NRs incorporated into chitosan (CHT) coating while ZnO NRs were not visible in the CHT 2%/ZnO NRs composite. XRD and FTIR results showed the presence of the ZnO and chitosan. The water contact angle decreased from 80° ± 2° (control) to 65° ± 2° for CHT 1%/ZnO NRs and 42 ± 2° for CHT 2%/ZnO NRs composite coatings. The antimicrobial activities of the coated fiberglass panels were investigated using biofilm-forming bacteria Bacillus subtilis and Escherichia coli under both light and dark conditions. CHT/ZnO composite coated fiberglass panels showed the strongest antimicrobial activity compared to chitosan, ZnO NRs coatings, and Zn-based antifouling paint in the experiments with B. subtilis and E. coli under light conditions. The highest antifouling activity was observed for CHT 2%/ZnO composites. CHT/ZnO composites can be good alternatives to the toxic antifouling paints.

Toxicity of Different Zinc Oxide Nanomaterials at 3 Trophic Levels: Implications for Development of Low-Toxicity Antifouling Agents.

Because zinc oxide (ZnO) nanomaterials are used in antifouling and antibacterial solutions, understanding their toxic effects on different aquatic organisms is essential. In the present study, we evaluated the toxicity of ZnO nanoparticles of 10 to 30 nm (ZnONPI) and 80 to 200 nm (ZnONPII), ZnO nanorods (width 80 nm, height 1.7 µm) attached to the support substrate (glass, ZnONRG) and not attached (ZnONRS), as well as Zn2+ ions at concentrations ranging from 0.5 to 100 mg/L. Toxicity was evaluated using the microalga Dunaliella salina, the brine shrimp Artemia salina, and the marine bacterium Bacillus cereus. The highest toxicity was observed for ZnONPs (median lethal concentration [LC50] ~15 mg/L) and Zn2+ ions (LC50 ~13 mg/L), whereas the lowest toxicity found for ZnO nanorods (ZnONRG LC50 ~60 mg/L; ZnONRS LC50 ~42 mg/L). The presence of the support substrate in case of ZnO nanorods reduced the associated toxicity to aquatic organisms. Smaller ZnONPs resulted in the highest Zn2+ ion dissolution among tested nanostructures. Different aquatic organisms responded differently to ZnO nanomaterials, with D. salina and B. cereus being more sensitive than A. salina. Toxicity of nanostructures increased with an increase of the dose and the time of exposure. Supported ZnO nanorods can be used as a low-toxicity alternative for future antimicrobial and antifouling applications. Environ Toxicol Chem 2020;39:1343-1354. © 2020 SETAC.

Free and partially encapsulated manganese ferrite nanoparticles in multiwall carbon nanotubes.

Free and partially encapsulated manganese ferrite (MnFe2O4) nanoparticles are synthesized and characterized regarding structure, surface, and electronic and magnetic properties. The preparation method of partially encapsulated manganese ferrite enables the formation of a hybrid nanoparticle/tube system, which exhibits properties of manganese ferrite nanoparticles inside and attached to the external surface of the tubes. The effect of having manganese ferrite nanoparticles inside the tubes is observed as a shift in the X-ray diffraction peaks and as an increase in stress, hyperfine field, and coercivity when compared to free manganese ferrite nanoparticles. On the other hand, a strong charge transfer from the multiwall carbon nanotubes is attributed to the attachment of manganese ferrite nanoparticles outside the tubes, which is detected by a significant decrease in the σ band emission of the ultraviolet photoemission spectroscopy signal. This is followed by an increase in the density of states at the Fermi level of the attached manganese ferrite nanoparticles in comparison to free manganese ferrite nanoparticles, which leads to an enhancement of the metallic properties.

Removal of heavy metal ions by capacitive deionization: Effect of surface modification on ions adsorption.

Activated carbon cloth (ACC) coated with zinc oxide (ZnO) nanoparticles (NPs) have been used as electrodes in flow-by capacitive deionization (CDI) system. Aqueous solution of individual Pb2+ and Cd2+ ions and mixed Pb2+ and Cd2+ ions were used as test contaminant in CDI system to study the effect of surface modification upon ions removal efficiency. Due to the aggregated structure of ZnO NPs on ACC surface, the modified ACC electrodes develop the additional surface area as well as dielectric barrier therefore resulting in higher specific capacitance. In addition, coating with ZnO NPs effectively reduced physical adsorption whereby enhanced the ions adsorption rate and capacity during electrosorption process. Upon incorporating with ZnO NPs, the electrosorption efficiency was enhanced from 17% to 33% for Pb2+, from 21% to 29% for Cd2+ and from 21% to 35% for mixed Pb2+ and Cd2+ ions. The power consumption of individual ions and mixed ions removal process for ACC and ZnO NPs modified ACC were also discussed. Furthermore, used ACC electrodes surfaces were examined using photoelectron spectroscopy (XPS) and results were also conferred. The CDI ACC electrodes with ZnO NPs showed a promising and an effective way for heavy metal removal applications.

An Easy-to-Use Tool for Modeling the Dynamics of Capacitive Deionization.

Capacitive deionization is an emerging method of desalinating brackish water that has been presented as an alternative to the widely applied technologies such as reverse osmosis. However, for the technology to find more widespread use, it is important not only to improve its efficiency but also to make its modeling more accessible for researchers. In this work, a program has been developed and provided as an open-source with which a user can simulate the performance of a capacitive deionization system by simply entering the basic experimental conditions. The usefulness of this program was demonstrated by predicting how the effluent concentration in a continuous-mode constant-voltage operation varies with time, as well as how it depends on the flow rate, applied voltage, and inlet ion concentration. Finally, the generality of the program has been demonstrated using data from reports in the literature wherein various electrode materials, cell structures, and operational modes were used. Thus, we conclude that the model, termed the dynamic Langmuir model, could be an effective and simple tool for modeling the dynamics of capacitive deionization.

Bioinspired nanocoatings for biofouling prevention by photocatalytic redox reactions.

Aquaculture is a billion dollar industry and biofouling of aquaculture installations has heavy economic penalties. The natural antifouling (AF) defence mechanism of some seaweed that inhibits biofouling by production of reactive oxygen species (ROS) inspired us to mimic this process by fabricating ZnO photocatalytic nanocoating. AF activity of fishing nets modified with ZnO nanocoating was compared with uncoated nets (control) and nets painted with copper-based AF paint. One month experiment in tropical waters showed that nanocoatings reduce abundances of microfouling organisms by 3-fold compared to the control and had higher antifouling performance over AF paint. Metagenomic analysis of prokaryotic and eukaryotic fouling organisms using next generation sequencing platform proved that nanocoatings compared to AF paint were not selectively enriching communities with the resistant and pathogenic species. The proposed bio-inspired nanocoating is an important contribution towards environmentally friendly AF technologies for aquaculture.

Self-decontaminating photocatalytic zinc oxide nanorod coatings for prevention of marine microfouling: a mesocosm study.

The antifouling (AF) properties of zinc oxide (ZnO) nanorod coated glass substrata were investigated in an out-door mesocosm experiment under natural sunlight (14:10 light: dark photoperiod) over a period of five days. The total bacterial density (a six-fold reduction) and viability (a three-fold reduction) was significantly reduced by nanocoatings in the presence of sunlight. In the absence of sunlight, coated and control substrata were colonized equally by bacteria. MiSeq Illumina sequencing of 16S rRNA genes revealed distinct bacterial communities on the nanocoated and control substrata in the presence and absence of light. Diatom communities also varied on nanocoated substrata in the presence and the absence of light. The observed AF activity of the ZnO nanocoatings is attributed to the formation of reactive oxygen species (ROS) through photocatalysis in the presence of sunlight. These nanocoatings are a significant step towards the production of an environmentally friendly AF coating that utilizes a sustainable supply of sunlight.

Antifouling properties of zinc oxide nanorod coatings.

In laboratory experiments, the antifouling (AF) properties of zinc oxide (ZnO) nanorod coatings were investigated using the marine bacterium Acinetobacter sp. AZ4C, larvae of the bryozoan Bugula neritina and the microalga Tetraselmis sp. ZnO nanorod coatings were fabricated on microscope glass substrata by a simple hydrothermal technique using two different molar concentrations (5 and 10 mM) of zinc precursors. These coatings were tested for 5 h under artificial sunlight (1060 W m(-2) or 530 W m(-2)) and in the dark (no irradiation). In the presence of light, both the ZnO nanorod coatings significantly reduced the density of Acinetobacter sp. AZ4C and Tetraselmis sp. in comparison to the control (microscope glass substratum without a ZnO coating). High mortality and low settlement of B. neritina larvae was observed on ZnO nanorod coatings subjected to light irradiation. In darkness, neither mortality nor enhanced settlement of larvae was observed. Larvae of B. neritina were not affected by Zn(2+) ions. The AF effect of the ZnO nanorod coatings was thus attributed to the reactive oxygen species (ROS) produced by photocatalysis. It was concluded that ZnO nanorod coatings effectively prevented marine micro and macrofouling in static conditions.

Enhancement in ion adsorption rate and desalination efficiency in a capacitive deionization cell through improved electric field distribution using electrodes composed of activated carbon cloth coated with zinc oxide nanorods.

Electrodes composed of activated carbon cloth (ACC) coated with zinc oxide (ZnO) nanorods are compared with plain ACC electrodes, with respect to their desalination efficiency of a 17 mM NaCl solution at different applied potentials. Polarization of the ZnO nanorods increased the penetration depth and strength of the electric field between the electrodes, leading to an increase in the capacitance and charge efficiency at reduced input charge ratios. Uniform distribution of the electric field lines between two electrodes coated with ZnO nanorods led to faster ion adsorption rates, reduced the electrode saturation time, and increased the average desalination efficiency by ∼45% for all applied potentials. The electrodes were characterized for active surface area, capacitance from cyclic voltammetry, theoretical assessment of surface area utilization, and the magnitude of electric field force acting on an ion of unit charge for each potential.

One pot synthesis of opposing 'rose petal' and 'lotus leaf' superhydrophobic materials with zinc oxide nanorods.

The synthesis in one pot(1) of opposing 'rose petal' and 'lotus leaf' superhydrophobic materials from commercially available superhydrophilic cloth substrates of varying texture is described for the first time. Surfaces of 'rough' textured cloth and 'smooth' textured cloth were simultaneously rendered superhydrophobic by growing zinc oxide (ZnO) nanorods by a hydrothermal process in the same chemical bath. Contact angle hysteresis and water pendant drop tests revealed strong water adhesion to ZnO microrod-treated rough cloth. The combination of water contact angle >150° and strong adhesion is indicative of the 'rose petal effect' with potential for water pinning. Smooth cloth with ZnO nanorods exhibited no adhesion to water droplets with facilitative roll-off. The combination of water contact angle >150° and weak to no adhesion with water is indicative of the 'lotus leaf effect' with potential for self-cleaning. Pendant water drop tests indicated cohesive failure of water on rough cloth coated with ZnO nanorods. Natural rose petals demonstrated adhesive failure between the petal surface and water droplet. A parsimonious explanation is presented. We also describe the development of superhydrophobic clothes without the need for special conditions or further chemical modification.

Role of central metal ions in hematoporphyrin-functionalized titania in solar energy conversion dynamics.

In this study, we have investigated the efficacy of electron transfer processes in hematoporphyrin (HP) and iron hematoporphyrin ((Fe)HP) sensitized titania as potential materials for capturing and storing solar energy. Steady-state and picosecond-resolved fluorescence studies show the efficient photoinduced electron transfer processes in hematoporphyrin-TiO2 (HP-TiO2) and Fe(III)-hematoporphyrin-TiO2 (Fe(III)HP-TiO2) nanohybrids, which reveal the role of central metal ions in electron transfer processes. The bidentate covalent attachment of HP onto TiO2 particulates is confirmed by FTIR, Raman scattering and X-ray photoelectron spectroscopy (XPS) studies. The iron oxidation states and the attachment of iron to porphyrin through pyrrole nitrogen atoms were investigated by cyclic voltammetry and FTIR studies, respectively. We also investigated the potential application of HP-TiO2 and Fe(III)HP-TiO2 nanohybrids for the photodegradation of a model organic pollutant methylene blue (MB) in aqueous solution under wavelength dependent light irradiation. To further investigate the role of iron oxidation states in electron transfer processes, photocurrent measurements were done by using Fe(III) and Fe(II) ions in porphyrin. This work demonstrates the role of central metal ions in fundamental electron transfer processes in porphyrin sensitized titania and their implications for dye-sensitized device performance.

Unusual surface and edge morphologies, sp2 to sp3 hybridized transformation and electronic damage after Ar+ ion irradiation of few-layer graphene surfaces.

Roughness and defects induced on few-layer graphene (FLG) irradiated by Ar+ ions at different energies were investigated using X-ray photoemission spectroscopy (XPS) and atomic force microscopy techniques. The results provide direct experimental evidence of ripple formation, sp2 to sp3 hybridized carbon transformation, electronic damage, Ar+ implantation, unusual defects and edge reconstructions in FLG, which depend on the irradiation energy. In addition, shadowing effects similar to those found in oblique-angle growth of thin films were seen. Reliable quantification of the transition from the sp2-bonding to sp3-hybridized state as a result of Ar+ ion irradiation is achieved from the deconvolution of the XPS C (1s) peak. Although the ion irradiation effect is demonstrated through the shape of the derivative of the Auger transition C KVV spectra, we show that the D parameter values obtained from these spectra which are normally used in the literature fail to account for the sp2 to sp3 hybridization transition. In contrast to what is known, it is revealed that using ion irradiation at large FLG sample tilt angles can lead to edge reconstructions. Furthermore, FLG irradiation by low energy of 0.25 keV can be a plausible way of peeling graphene layers without the need of Joule heating reported previously.

Superhydrophobic surfaces using selected zinc oxide microrod growth on ink-jetted patterns.

The synthesis and properties of superhydrophobic surfaces based on binary surface topography made of zinc oxide (ZnO) microrod-decorated micropatterns are reported. ZnO is intrinsically hydrophilic but can be utilized to create hydrophobic surfaces by creating artificial roughness via microstructuring. Micron scale patterns consisting of nanocrystalline ZnO seed particles were applied to glass substrates with a modified ink-jet printer. Microrods were then grown on the patterns by a hydrothermal process without any further chemical modification. Water contact angle (WCA)(1) up to 153° was achieved. Different micro array patterned surfaces with varying response of static contact angle or sessile droplet analysis are reported.

Enhanced visible light photocatalysis through fast crystallization of zinc oxide nanorods.

Hydrothermally grown ZnO nanorods have inherent crystalline defects primarily due to oxygen vacancies that enhance optical absorption in the visible spectrum, opening up possibilities for visible light photocatalysis. Comparison of photocatalytic activity of ZnO nanorods and nanoparticle films on a test contaminant methylene blue with visible light irradiation at 72 kilolux (klx) showed that ZnO nanorods are 12-24% more active than ZnO nanoparticulate films. This can be directly attributed to the increased effective surface area for adsorption of target contaminant molecules. Defects, in the form of interstitials and vacancies, were intentionally created by faster growth of the nanorods by microwave activation. Visible light photocatalytic activity was observed to improve by ≈8% attributed to the availability of more electron deficient sites on the nanorod surfaces. Engineered defect creation in nanostructured photocatalysts could be an attractive solution for visible light photocatalysis.