This paper presents the application of zinc/aluminium-layered double hydroxide-quinclorac (Zn/Al-LDH-QC) as a modifier of multiwalled carbon nanotubes (MWCNT) paste electrode for the determination of bisphenol A (BPA). The Zn/Al-LDH-QC/MWCNT morphology was examined by a transmission electron microscope and a scanning electron microscope. Electrochemical impedance spectroscopy was utilized to investigate the electrode interfacial properties. The electrochemical responses of the modified electrode towards BPA were thoroughly evaluated by using square-wave voltammetry technique. The electrode demonstrated three linear plots of BPA concentrations from 3.0 × 10-8⁻7.0 × 10-7 M (R² = 0.9876), 1.0 × 10-6⁻1.0 × 10-5 M (R² = 0.9836) and 3.0 × 10-5⁻3.0 × 10-4 M (R² = 0.9827) with a limit of detection of 4.4 × 10-9 M. The electrode also demonstrated good reproducibility and stability up to one month. The presence of several metal ions and organic did not affect the electrochemical response of BPA. The electrode is also applicable for BPA determination in baby bottle and mineral water samples with a range of recovery between 98.22% and 101.02%.
Jicama peroxidase (JP) was covalently immobilized onto functionalized multi-walled carbon nanotube (MWCNT) Buckypaper/Polyvinyl alcohol (BP/PVA) membrane and employed for degradation of methylene blue dye. The parameters of the isotherm and kinetic models are estimating using ant colony optimization (ACO), which do not meddle the non-linearity form of the respective models. The proposed inverse modelling through ACO optimization was implemented, and the parameters were evaluated to minimize the non-linear error functions. The adsorption of MB dye onto JP-immobilized BP/PVA membrane follows Freundlich isotherm model (R2 = 0.99) and the pseudo 1st order or 2nd kinetic model (R2 = 0.980 & 0.968 respectively). The model predictions from the parameters estimated by ACO resulted values close the experimental values, thus inferring that this approach captured the inherent characteristics of MB adsorption. Moreover, the thermodynamic studies indicated that the adsorption was favourable, spontaneous, and exothermic in nature. The comprehensive structural analyses have confirmed the successful binding of peroxidase onto BP/PVA membrane, as well as the effective MB dye removal using immobilized JP membrane. Compared to BP/PVA membrane, the reusability test revealed that JP-immobilized BP/PVA membrane has better dye removal performances as it can retain 64% of its dye removal efficiency even after eight consecutive cycles. Therefore, the experimental results along with modelling results demonstrated that JP-immobilized BP/PVA membrane is expected to bring notable impacts for the development of effective green and sustainable wastewater treatment technologies.
Flexible plastic packaging waste causes serious environmental issues due to challenges in recycling. This study investigated the conversion of flexible plastic packaging waste with 11.8 and 27.5 wt.% polyethylene terephthalate (PET) (denoted as PET-12 and PET-28, respectively) into oil and multi-walled carbon nanotubes (MWCNTs). The mixtures were initially pyrolyzed and the produced volatiles were processed over 9.0 wt.% Fe2O3 supported on ZSM-5 (400 °C) to remove oxygenated hydrocarbons (catalytic cracking of terephthalic and benzoic acids) that deteriorate oil quality. The contents of oxygenated hydrocarbons were decreased in oil from 4.6 and 9.4 wt.% per mass of PET-12 and PET-28, respectively, to undetectable levels. After catalytic cracking, the oil samples had similar contents of gasoline, diesel and heavy oil/wax fractions. The non-condensable gas was converted into MWCNTs over 0.9 wt.% Ni supported on CaCO3 (700 °C). The type of plastic packaging influenced the yields (2.4 and 1.5 wt.% per mass of PET-12 and PET-28, respectively) and the properties of MWCNTs due to the differences in gas composition. Regarding the electrocatalytic application, both MWCNTs from PET-12 and PET-28 outperformed commercial MWCNTs and Pt-based electrodes during oxygen evolution reaction, suggesting that MWCNTs from flexible plastic packaging can potentially replace conventional electrode materials.
Since the complexity of photocatalyst synthesis process and high cost of noble cocatalyst leftovers a major hurdle to producing hydrogen (H2) from water, a noble metal-free Ni-Si/MgO photocatalyst was realized for the first time to generate H2 effectively under illumination with visible light. The catalyst was produced by means of simple one-pot solid reaction using self-designed metal reactor. The physiochemical properties of photocatalyst were identified by XRD, FESEM, HRTEM, EDX, UV-visible, XPS, GC and PL. The photocatalytic activities of Ni-Si/MgO photocatalyst at different nickel concentrations were evaluated without adjusting pH, applied voltage, sacrificial agent or electron donor. The ultrathin-nanosheet with hierarchically porous structure of catalyst was found to exhibit higher photocatalytic H2 production than hexagonal nanorods structured catalyst, which suggests that the randomly branched nanosheets are more active surface to increase the light-harvesting efficiency due to its short electron diffusion path. The catalyst exhibited remarkable performance reaching up to 714 µmolh-1 which is higher among the predominant semiconductor catalyst. The results demonstrated that the photocatalytic reaction irradiated under visible light illumination through the production of hydrogen and hydroxyl radicals on metals. The outcome indicates an important step forward one-pot facile approach to prepare noble ultrathin photocatalyst for hydrogen production from water.
This article provides an overview of the structural and physicochemical properties of stable carbon-based nanomaterials and their applications as counter electrodes (CEs) in dye-sensitized solar cells (DSSCs). The research community has long sought to harvest highly efficient third-generation DSSCs by developing carbon-based CEs, which are among the most important components of DSSCs. Since the initial introduction of DSSCs, Pt-based electrodes have been commonly used as CEs owing to their high-electrocatalytic activities, thus, accelerating the redox couple at the electrode/electrolyte interface to complete the circuit. However, Pt-based electrodes have several limitations due to their cost, abundance, complicated facility, and low corrosion resistance in a liquid electrolyte, which further restricts the large-area applications of DSSCs. Although carbon-based nanostructures showed the best potential to replace Pt-CE of DSSC, several new properties and characteristics of carbon-CE have been reported for future enhancements in this field. In this review, we discuss the detailed synthesis, properties, and performances of various carbonaceous materials proposed for DSSC-CE. These nano-carbon materials include carbon nanoparticles, activated carbon, carbon nanofibers, carbon nanotube, two-dimensional graphene, and hybrid carbon material composites. Among the CE materials currently available, carbon-carbon hybridized electrodes show the best performance efficiency (up to 10.05%) with a high fill factor (83%). Indeed, up to 8.23% improvements in cell efficiency may be achieved by a carbon-metal hybrid material under sun condition. This review then provides guidance on how to choose appropriate carbon nanomaterials to improve the performance of CEs used in DSSCs.
Efficient solar driven photoelectrochemical (PEC) response by enhancing charge separation has attracted great interest in the hydrogen generation application. The formation of one-dimensional ZnO nanorod structure without bundling is essential for high efficiency in PEC response. In this present research work, ZnO nanorod with an average 500 nm in length and average diameter of about 75 nm was successfully formed via electrodeposition method in 0.05 mM ZnCl₂ and 0.1 M KCl electrolyte at 1 V for 60 min under 70 °C condition. Continuous efforts have been exerted to further improve the solar driven PEC response by incorporating an optimum content of TiO₂ into ZnO nanorod using dip-coating technique. It was found that 0.25 at % of TiO₂ loaded on ZnO nanorod film demonstrated a maximum photocurrent density of 19.78 mA/cm² (with V vs. Ag/AgCl) under UV illumination and 14.75 mA/cm² (with V vs. Ag/AgCl) under solar illumination with photoconversion efficiency ~2.9% (UV illumination) and ~4.3% (solar illumination). This performance was approximately 3-4 times higher than ZnO film itself. An enhancement of photocurrent density and photoconversion efficiency occurred due to the sufficient Ti element within TiO₂-ZnO nanorod film, which acted as an effective mediator to trap the photo-induced electrons and minimize the recombination of charge carriers. Besides, phenomenon of charge-separation effect at type-II band alignment of Zn and Ti could further enhance the charge carrier transportation during illumination.
WO₃-decorated TiO₂ nanotube arrays were successfully synthesized using an in situ anodization method in ethylene glycol electrolyte with dissolved H₂O₂ and ammonium fluoride in amounts ranging from 0 to 0.5 wt %. Anodization was carried out at a voltage of 40 V for a duration of 60 min. By using the less stable tungsten as the cathode material instead of the conventionally used platinum electrode, tungsten will form dissolved ions (W(6+)) in the electrolyte which will then move toward the titanium foil and form a coherent deposit on the titanium foil. The fluoride ion content was controlled to determine the optimum chemical dissolution rate of TiO₂ during anodization to produce a uniform nanotubular structure of TiO₂ film. Nanotube arrays were then characterized using FESEM, EDAX, XRD, as well as Raman spectroscopy. Based on the FESEM images obtained, nanotube arrays with an average pore diameter of up to 65 nm and a length of 1.8 µm were produced. The tungsten element in the samples was confirmed by EDAX results which showed varying tungsten content from 0.22 to 2.30 at%. XRD and Raman results showed the anatase phase of TiO₂ after calcination at 400 °C for 4 h in air atmosphere. The mercury removal efficiency of the nanotube arrays was investigated by photoirradiating samples dipped in mercury chloride solution with TUV (Tube ultraviolet) 96W UV-B Germicidal light. The nanotubes with the highest aspect ratio (15.9) and geometric surface area factor (92.0) exhibited the best mercury removal performance due to a larger active surface area, which enables more Hg(2+) to adsorb onto the catalyst surface to undergo reduction to Hg⁰. The incorporation of WO₃ species onto TiO₂ nanotubes also improved the mercury removal performance due to improved charge separation and decreased charge carrier recombination because of the charge transfer from the conduction band of TiO₂ to the conduction band of WO₃.
Palm kernel cake (PKC) is the solid residue following oil extraction of palm kernels and useful to fatten animals either as a single feed with only minerals and vitamins supplementation, or mixed with other feedstuffs such as corn kernels or soy beans. The occurrence of mycotoxins (aflatoxins, ochratoxins, zearalenone, and fumonisins) in feed samples affects the animal's health and also serves as a secondary contamination to humans via consumption of eggs, milk and meats. Of these, aflatoxin B₁ (AFB₁) is the most toxically potent and a confirmed carcinogen to both humans and animals. Methods such as High Performance Liquid Chromatography (HPLC) and Liquid Chromatography-Mass Spectrometry (LC-MS/MS) are common in the determination of mycotoxins. However, these methods usually require sample pre-treatment, extensive cleanup and skilled operator. Therefore, in the present work, a rapid method of electrochemical immunosensor for the detection of AFB₁ was developed based on an indirect competitive enzyme-linked immunosorbent assay (ELISA). Multi-walled carbon nanotubes (MWCNT) and chitosan (CS) were used as the electrode modifier for signal enhancement.N-ethyl-N'-(3-dimethylaminopropyl)-carbodiimide (EDC) andN-hydroxysuccinimide (NHS) activated the carboxyl groups at the surface of nanocomposite for the attachment of AFB₁-BSA antigen by covalent bonding. An indirect competitive reaction occurred between AFB₁-BSA and free AFB₁ for the binding site of a fixed amount of anti-AFB₁ antibody. A catalytic signal based on horseradish peroxidase (HRP) in the presence of hydrogen peroxide (H₂O₂) and 3,3',5,5'-tetramethylbenzidine (TMB) mediator was observed as a result of attachment of the secondary antibody to the immunoassay system. As a result, the reduction peak of TMB(Ox)was measured by using differential pulse voltammetry (DPV) analysis. Based on the results, the electrochemical surface area was increased from 0.396 cm² to 1.298 cm² due to the electrode modification with MWCNT/CS. At the optimal conditions, the working range of the electrochemical immunosensor was from 0.0001 to 10 ng/mL with limit of detection of 0.1 pg/mL. Good recoveries were obtained for the detection of spiked feed samples (PKC, corn kernels, soy beans). The developed method could be used for the screening of AFB₁ in real samples.
Carbon nanotubes (CNTs) reinforced with gold nanoparticles (AuNPs) and chitosan nanoparticles (CTSNPs) were anchored on a screen-printed electrode to fabricate a multi-walled structure for the detection of quinoline. The surface morphology of the nanocomposites and the modified electrode was examined by an ultra-high resolution field emission scanning electron microscope (FESEM), and Fourier-transform infrared (FT-IR) spectroscopy was used to confirm the presence of specific functional groups on the multi-walled carbon nanotubes MWCNTs. Cyclic voltammetry (CV) and linear sweep voltammetry (LSV) were used to monitor the layer-by-layer assembly of ultra-thin films of nanocomposites on the surface of the electrode and other electrochemical characterizations. Under optimized conditions, the novel sensor displayed outstanding electrochemical reactivity towards the electro-oxidation of quinoline. The linear range was fixed between 0.0004 and 1.0 μM, with a limit of detection (LOD) of 3.75 nM. The fabricated electrode exhibited high stability with excellent sensitivity and selectivity, specifically attributable to the salient characteristics of AuNPs, CTSNPs, and MWCNTs and the synergistic inter-relationship between them. The newly developed electrode was tested in the field. The Ipa increased with an increase in the amount of quinoline solution added, and the peak potential deviated minimally, depicting the real capability of the newly fabricated electrode.
Photocatalysis is an ecofriendly technique that emerged as a promising alternative for the degradation of many organic pollutants. The weaknesses of the present photocatalytic system which limit their industrial applications include low-usage of visible light, fast charge recombination, and low migration ability of the photo-generated electrons and holes. Therefore, various elements such as noble metals and transition metals as well as non-metals and metalloids (i.e., graphene, carbon nanotube, and carbon quantum dots) are doped into the photocatalyst as co-catalysts to enhance the photodegradation performance. The incorporation of the co-catalyst which alters the photocatalytic mechanism was discussed in detail. The application of photocatalysts in treating persistent organic pollutants such as pesticide, pharmaceutical compounds, oil and grease and textile in real wastewater was also discussed. Besides, a few photocatalytic reactors in pilot scale had been designed for the effort of commercializing the system. In addition, hybrid photocatalytic system integrating with membrane filtration together with their membrane fabrication methods had also been reviewed. This review outlined various types of heterogeneous photocatalysts, mechanism, synthesis methods of biomass supported photocatalyst, photocatalytic degradation of organic substances in real wastewater, and photocatalytic reactor designs and their operating parameters as well as the latest development of photocatalyst incorporated membrane.
This paper presents the findings of a study on adsorption of dichlorodiphenythreechloroethen (DDT) and polychlorinated biphenyls (PCBs) on three nanomaterials including Multi walled Carbon Nanotube (MWNT), nano-clay and nano-alumina. DDT and PCBs are of significant concern due their high toxicity and long environmental half-lives. Experiments were conducted using batch adsorption procedures at different DDT and PCBs concentrations, from 10 to 60 mg/L. The amounts of MWNT, nano-clay and Nano-alumina used were 0.25%, 0.50%, 0.75%, 1%, 2% and 10%. The adsorption of PCBs solution onto the MWNT, nano-clay and nano-alumina was characterized by an initial rapid adsorption which eventually became constant within 22, 20, and 17 hours, respectively. The adsorption of DDT solution onto the MWNT, nano-clay and nano-alumina was also characterized by an initial rapid adsorption which gradually became constant within 22, 22 and 16 hours, respectively. Results of this study indicated that MWNT was a better adsorbent material compared to nano-clay and nano-alumina for both contaminants in this study. While at 10% of MWNT 88.9% and 77% of DDT and PCB were removed by MWNT, respectively. The effect of pH and temperature were also investigated.
In this study, an electrochemical sensor was fabricated based on gold nanoparticles/ ethylenediamine/ multi-wall carbon-nanotubes modified gold electrode (AuNPs/en/MWCNTs/AuE) for determination of valrubicin in biological samples. Valrubicin was effectively accumulated on the surface of AuNPs/en/MWCNTs/AuE and produced a pair of redox peaks at around 0.662 and 0.578V (vs. Ag/AgCl) in citrate buffer (pH4.0). The electrochemical parameters including pH, buffer, ionic strength, scan rate and size of AuNPs have been optimized. There was a good linear correlation between cathodic peak current and concentration of valrubicin in the range of 0.5 to 80.0μmolL(-1) with the detection limit of 0.018μmolL(-1) in citrate buffer (pH4.0) and 0.1molL(-1) KCl. Finally, the constructed sensor was successfully applied for determination of valrubicin in human urine and blood serum. In further studies, the different sequences of single stranded DNA probes have been immobilized on the surface of AuNPs decorated on MWCNTs to study the interaction of oligonucleotides with valrubicin.
The progress of novel sorbents and their function in preconcentration techniques for determination of trace elements is a topic of great importance. This review discusses numerous analytical approaches including the preparation and practice of unique modification of solid-phase materials. The performance and main features of ion-imprinting polymers, carbon nanotubes, biosorbents, and nanoparticles are described, covering the period 2007-2012. The perspective and future developments in the use of these materials are illustrated.
Polypyrrole multi-walled carbon nanotube composite layers were used to modify the gold layer to measure heavy metal ions using the surface plasmon resonance technique. The new sensor was fabricated to detect trace amounts of mercury (Hg), lead (Pb), and iron (Fe) ions. In the present research, the sensitivity of a polypyrrole multi-walled carbon nanotube composite layer and a polypyrrole layer were compared. The application of polypyrrole multi-walled carbon nanotubes enhanced the sensitivity and accuracy of the sensor for detecting ions in an aqueous solution due to the binding of mercury, lead, and iron ions to the sensing layer. The Hg ion bonded to the sensing layer more strongly than did the Pb and Fe ions. The limitation of the sensor was calculated to be about 0.1 ppm, which produced an angle shift in the region of 0.3° to 0.6°.
This paper presents the development of novel alternative injectable calcium phosphate cement (CPC) composites for orthopaedic applications. The new CPC composites comprise β-tri-calcium phosphate (β-TCP) and di-calcium phosphate anhydrous (DCPA) mixed with bovine serum albumin (BSA) and incorporated with multi-walled carbon nanotubes (MWCNTs) or functionalized MWCNTs (MWCNTs-OH and MWCNTs-COOH). Scanning electron microscopy (SEM), compressive strength tests, injectability tests, Fourier transform infrared spectroscopy and X-ray diffraction were used to evaluate the properties of the final products. Compressive strength tests and SEM observations demonstrated particularly that the concomitant admixture of BSA and MWCNT improved the mechanical properties, resulting in stronger CPC composites. The presence of MWCNTs and BSA influenced the morphology of the hydroxyapatite (HA) crystals in the CPC matrix. BSA was found to act as a promoter of HA growth when bounded to the surface of CPC grains. MWCNT-OH-containing composites exhibited the highest compressive strengths (16.3 MPa), being in the range of values for trabecular bone (2-12 MPa).
A novel microextraction technique termed solid phase membrane tip extraction (SPMTE) was developed. Selected triazine herbicides were employed as model compounds to evaluate the extraction performance and multiwall carbon nanotubes (MWCNTs) were used as the adsorbent enclosed in SPMTE device. The SPMTE procedure was performed in semi-automated dynamic mode and several important extraction parameters were comprehensively optimized. Under the optimum extraction conditions, the method showed good linearity in the range of 1-100 microg/L, acceptable reproducibility (RSD 6-8%, n=5), low limits of detection (0.2-0.5 microg/L), and satisfactory relative recoveries (95-101%). The SPMTE device could be regenerated and reused up to 15 analyses with no analyte carry-over effects observed. Comparison was made with commercially available solid phase extraction-molecular imprinted polymer cartridge (SPE-MIP) for triazine herbicides as the reference method. The new developed method showed comparable or even better results against reference method and is a simple, feasible, and cost effective microextraction technique.
Applying nanotechnology to deliver drug could result in several benefits such as prolong duration of action, enhancement in overall bioavailability, targeting to specific site, low initial loading dose require, systemic stability enhancement etc. Halloysite is one of those clay minerals showing maximum effectiveness when consider as a nano drug carriers for different kind applications. Here, we have used norfloxacin as the model drug for loading into halloysite nanotube (HNT) for its anti-bacterial activity. Norfloxacin was loaded into halloysites by vacuum operation and sonication. The nanotubes were evaluated using X-ray diffraction (XRD), Fourier-transform infrared spectroscopy (FTIR), transmission electron microscopy (TEM), scanning electron microscopy (SEM), optical microscopy, water absorption studies, cytotoxicity studies, antimicrobial studies and in vitro diffusion studies. SEM, FT-IR and XRD analysis data showed that the norfloxacin was successfully loaded into nanotubes. TEM analysis confirmed loading of norfloxacin in halloysites' lumen. The halloysite/chitosan nanocomposites were prepared by solvent casting and freeze-drying method. SEM analysis revealed compact and rugged surface of nanocomposites due to existing norfloxacin loaded halloysite. FTIR and XRD confirmed formation of nanocomposite. The nanocomposites showed good antimicrobial effect and good biocompatibility in cytotoxicity study. The in-vitro release studies revealed that halloysite/chitosan nanocomposites were able to sustain the drug release. Also, the nanocomposites were stable in various humidity conditions. Therefore, all the outcomes suggest that the prepared nanocomposites can provide enhanced therapeutic benefits and they can be very potential nano vehicle for sustaining drug delivery.
Magnetic beads (AO-γ-Fe2O3) of alginate (A) impregnated with citrate coated maghemite nanoparticles (γ-Fe2O3) and oxidized multiwalled carbon nanotubes (OMWCNTs) were synthesized and used as adsorbent for the removal of methylene blue from water. The XRD analysis revealed that the diameter of γ-Fe2O3 is 10.24 nm. The mass saturation magnetization of AO-γ-Fe2O3 and γ-Fe2O3 were found to be 27.16 and 42.63 emu·g-1, respectively. The adsorption studies revealed that the data of MB isotherm were well fitted to the Freundlich model. The Langmuir isotherm model exhibited a maximum adsorption capacity of 905.5 mg·g-1. The adsorption was very dependent on initial concentration, adsorbent dose, and temperature. The beads exhibited high adsorption stability in large domain of pH (4-10). The thermodynamic parameters determined at 283, 293, 303, and 313 K revealed that the adsorption occurring was spontaneous and endothermic in nature. Adsorption kinetic data followed the intraparticle diffusion model. The AO-γ-Fe2O3 beads were used for six cycles without significant adsorptive performance loss. Therefore, the eco-friendly prepared AO-γ-Fe2O3 beads were considered as highly recyclable and efficient adsorbent for methylene blue as they can be easily separated from water after treatment.
Thiol-functionalized magnetic carbon nanotubes (TMCNTs) were employed as the sorbent in the magnetic micro-solid phase extraction (M-µ-SPE) of sulfonamide antibiotics (SAs) in water, milks and chicken meat products prior to high performance liquid chromatography-diode array detector (HPLC-DAD) analysis. The synthesized sorbent was characterized by several spectroscopic techniques. Optimum conditions were: 20 mg of TMCNTs at pH 4, 2 min extraction time, 10% addition of salt and 30 mL of sample volume. Under the optimized TMCNTs-M-µ-SPE and HPLC-DAD conditions, the method showed good linearity in the range of 0.1-500 µg L-1 (r2 ≥ 0.9950), low limits of detection (0.02-1.5 µg L-1), good analytes recovery (80.7-116.2%) and acceptable RSDs (0.3-7.7%, n = 15). The method was applied to tap water (1), milks (15) and commercial chicken meat products (35), SAs were detected in five chicken meat samples (3.0-25.7 µg L-1). The method is critically compared to those reported in the literature.
Rapid detection of foodborne pathogens is crucial as ingestion of contaminated food products may endanger human health. Thus, the objective of this study was to develop a biosensor using reduced graphene oxide-carbon nanotubes (rGO-CNT) nanocomposite via the hydrothermal method for accurate and rapid label-free electrochemical detection of pathogenic bacteria such as Salmonella enterica. The rGO-CNT nanocomposite was characterized using Fourier transform infrared spectroscopy, Raman spectroscopy, X-ray diffraction and transmission electron microscopy. The nanocomposite was dropped cast on the glassy carbon electrode and further modified with amino-modified DNA aptamer. The resultant ssDNA/rGO-CNT/GCE aptasensor was then used to detect bacteria by using differential pulse voltammetry (DPV) technique. Synergistic effects of aptasensor was evident through the combination of enhanced electrical properties and facile chemical functionality of both rGO and CNT for the stable interface. Under optimal experimental conditions, the aptasensor could detect S. Typhimurium in a wide linear dynamic range from 101 until 108 cfu mL-1 with a 101 cfu mL-1 of the limit of detection. This aptasensor also showed good sensitivity, selectivity and specificity for the detection of microorganisms. Furthermore, we have successfully applied the aptasensor for S. Typhimurium detection in real food samples.