The nickel (Ni) nanocrystals (average diameter 9.7+/-2.3nm) were deposited onto composite graphite electrode from a plating solution of 5.0mM NiCl(2)6H(2)O and 1.0M NH(4)Cl using scan rate of 6500mVs(-1). The initial potential -1.5V and final potential -0.5V vs. Ag/AgCl with applied time 120s were used for the whole deposition process. The variations of applied overpotentials and deposition times have affected the characteristics of Ni nanocrystals. It was found that the structural formation of Ni nanocrystals obtained were almost pure hexagonal close-packed (hcp). This study has demonstrated that the tuning of the final size, morphology and structural formation of the Ni nanocrystal were affected by control of nucleation, growth and hydrogen evolution processes in fast scan voltammetry technique used.
In this study, we synthesized covalently functionalized graphene nanoplatelet (GNP) aqueous suspensions that are highly stable and environmentally friendly for use as coolants in heat transfer systems. We evaluated the heat transfer and hydrodynamic properties of these nano-coolants flowing through a horizontal stainless steel tube subjected to a uniform heat flux at its outer surface. The GNPs functionalized with clove buds using the one-pot technique. We characterized the clove-treated GNPs (CGNPs) using X-ray photoelectron spectroscopy (XPS) and transmission electron microscopy (TEM). We then dispersed the CGNPs in distilled water at three particle concentrations (0.025, 0.075 and 0.1wt%) in order to prepare the CGNP-water nanofluids (nano-coolants). We used ultraviolet-visible (UV-vis) spectroscopy to examine the stability and solubility of the CGNPs in the distilled water. There is significant enhancement in thermo-physical properties of CGNPs nanofluids relative those for distilled water. We validated our experimental set-up by comparing the friction factor and Nusselt number for distilled water obtained from experiments with those determined from empirical correlations, indeed, our experimental set-up is reliable and produces results with reasonable accuracy. We conducted heat transfer experiments for the CGNP-water nano-coolants flowing through the horizontal heated tube in fully developed turbulent condition. Our results are indeed promising since there is a significant enhancement in the Nusselt number and convective heat transfer coefficient for the CGNP-water nanofluids, with only a negligible increase in the friction factor and pumping power. More importantly, we found that there is a significant increase in the performance index, which is a positive indicator that our nanofluids have potential to substitute conventional coolants in heat transfer systems because of their overall thermal performance and energy savings benefits.
The effect of metal cations, both nonhydrolyzable and hydrolyzable, on the zeta potential of palm olein emulsions stabilized by the nonionic emulsifier, polyoxyethylene nonyl phenyl ether, was investigated as a function of pH and cation concentrations, respectively. The oil drops were found to be negatively charged in the presence of simple mono- and divalent cations. Charge reversal of the oil drops was observed when hydrolyzable cations (Zn2+, Cu2+, Fe3+, and Al3+) were used and the behavior is strongly dependent on the type of cation, its concentration, and the pH of the dispersion. The results are discussed in terms of current theories of electrophoresis and adsorption-precipitation at interfaces. The chemical free energies of adsorption of the cations were calculated. Copyright 1999 Academic Press.
Due to the interestingly tolerated physicochemical properties of deep eutectic solvents (DESs), they are currently in the process of becoming widely used in many fields of science. Herein, we present a novel Hg(2+) adsorbent that is based on carbon nanotubes (CNTs) functionalized by DESs. A DES formed from tetra-n-butyl ammonium bromide (TBAB) and glycerol (Gly) was used as a functionalization agent for CNTs. This novel adsorbent was characterized using Raman spectroscopy, Fourier transform infrared (FTIR) spectroscopy, XRD, FESEM, EDX, BET surface area, and Zeta potential. Later, Hg(2+) adsorption conditions were optimized using response surface methodology (RSM). A pseudo-second order model accurately described the adsorption of Hg(2+). The Langmuir and Freundlich isotherm models described the absorption of Hg(2+) on the novel adsorbent with acceptable accuracy. The maximum adsorption capacity was found to be 177.76mg/g.
Iron and 4-(methylamino)benzoic acid have been successfully incorporated into silica extracted from rice husk. The silica/Fe/amine complex, RH-Fe(5% amine), showed a ca. 24% increase in specific surface area compared to RH-Fe. This increase was attributed to the templated formation of regular pores. The XRD showed the RH-Fe(5% amine) to be amorphous. The Friedel-Crafts benzylation reaction with toluene using RH-Fe(5% amine) showed a drastic reduction in the di-substituted products to ca. 1.0%.
The effect of pH and redox potential on the redox equilibria of iron oxides in aqueous-based magnetite dispersions was investigated. The ionic activities of each dissolved iron species in equilibrium with magnetite nanoparticles were determined and contoured within the Eh-pH framework of a composite stability diagram. Both standard redox potentials and equilibrium constants for all major iron oxide redox equilibria in magnetite dispersions were found to differ from values reported for noncolloidal systems. The "triple point" position of redox equilibrium among Fe(II) ions, magnetite, and hematite shifted to a higher standard redox potential and an equilibrium constant which was several orders of magnitude higher. The predominant area of magnetite stability was enlarged to cover a wider range of both pH and redox potentials as compared to that of a noncolloidal magnetite system.
As sulfate-radical (SR)-based advanced oxidation processes are increasingly implemented, Oxone has been frequently-used for generation of SR. While Co3O4 nanoparticle (NP) has been widely-accepted as a promising catalyst for activating Oxone, Co3O4 NPs tend to aggregate in water, losing their reactivity. Thus, many attempts have immobilized Co3O4 NPs on supports, especially carbonaceous substrates, because combination of Co NPs with carbon substrates offers synergistic effects for boosting catalytic activities. Moreover, carbon substrates doped with hetero-atoms (N and S) further increase electron transfer and reactivity. Therefore, it is even promising to immobilize Co NPs onto N/S-doped carbon (NSC) to form Co-embedded NSC (denoted as CoNSC) for enhancing Oxone activation. In this study, a convenient and facile technique is proposed to prepare such a CoNSC via a simple carbonization treatment of a coordination polymer of Co and trithiocyanuric acid (TTCA). The resulting CoNSC exhibits the sheet-like hexagonal morphology with the core-shell configuration, and Co NPs are well-embedded into the N/S-doped carbonaceous matrix, making it an advantageous heterogeneous catalyst for Oxone activation. As Azorubine S (ARS) decolorization is employed as a model reaction of Oxone activation, CoNSC exhibits a higher catalytic activity than pristine Co3O4 and NSC for Oxone activation to decolorize ARS. In comparison to the other reported catalysts, CoNSC also possesses a much lower Ea for ARS decolorization. CoNSC can be also reusable and stable for Oxone activation over multiple cycles without loss of catalytic activity. These features validate that CoNSC is a promising and useful Co-based catalyst for Oxone activation.
While transition metals are useful for activating monopersulfate (MPS) to degrade contaminants, bimetallic alloys exhibit stronger catalytic activities owing to several favorable effects. Therefore, even though Co is an efficient metal for MPS activation, CoFe alloys are even more promising heterogeneous catalysts for MPS activation. Immobilization/embedment of CoFe alloy nanoparticles (NPs) onto hetero-atom-doped carbon matrices appears as a practical strategy for evenly dispersing CoFe NPs and enhancing catalytic activities via interfacial synergies between CoFe and carbon. Herein, N-doped carbon-embedded CoFe alloy (NCCF) is fabricated here to exhibit a unique hollow-engineered nanostructure and the composition of CoFe alloy by using Co-ZIF as a precursor after the facile etching and Fe doping. The Fe dopant embeds CoFe alloy NPs into the hollow-structured N-doped carbon substrate, enabling NCCF to possess the higher mesoscale porosity, active N species as well as more superior electrochemical properties than its analogue without Fe dopants, carbon matrix-supported cobalt (NCCo). Thus, NCCF exhibits a considerably larger activity than NCCo and the benchmark catalyst, Co3O4 NP, for MPS activation to degrade an environmental hormone, dihydroxydiphenyl ketone (DHPK). Besides, NCCF + MPS shows an even lower activation energy for DHPK degradation than literatures, and retains its high efficiency for eliminating DHPK in different water media. DHPK degradation pathway and ecotoxicity assessment are unraveled based on the insights from the computational chemistry, demonstrating that DHPK degradation by NCCF + MPS did not result in the formation of toxic and highly toxic by-products. These features make NCCF a promising heterogeneous catalyst for MPS activation to degrade DHPK.
Nickel-substituted copper ferrite nanoparticles (NP) (Cu1-xNixFe2O4) were prepared using a cost-effective hydrothermal method. X-ray diffraction (XRD) pattern revealed a single-phase cubic spinel structure. The increase in lattice parameters and decrease in crystallite size are associated with the replacement of Cu ions by Ni ions in the host lattice of copper ferrite. The optimized Cu0.95Ni0.05Fe2O4 composition was subsequently annealed at 750 °C and 850 °C for further studies. Fourier transform infrared (FT-IR) analysis shows the existence of two promising fundamental adsorption peaks at 465 and 582 cm-1, related to the metal ion stretching vibrations at the tetrahedral (A) and octahedral (B) sites, respectively. The local disorder at both the A and B sublattices upon the incorporation of Ni was observed from the Raman analysis. Scanning electron microscopy (SEM) and high-resolution transmission electron microscopy (HR-TEM) images shows the formation of agglomerates composed of nano-sized spherical particles. A high Barrett-Joyner-Halenda (BJH) surface area was achieved 17.25 m2/g with a particle stability of -11.1 mV obtained by the zeta potential. Both the dielectric loss and dielectric constant are decreased, whereas the AC conductivity gets increased with increasing frequency. The magnetization-field hysteresis curves exhibited ferromagnetic behavior with a pseudo-single domain, and the cyclic voltammetry study revealed a pseudocapacitive trend. This study highlights the importance of Ni substitution to control the physicochemical properties of spinel-phase CuFe2O4 for diverse applications, such as energy storage and lithium-ion batteries.
In this study, we propose an innovative, bio-based, environmentally friendly approach for the covalent functionalization of multi-walled carbon nanotubes using clove buds. This approach is innovative because we do not use toxic and hazardous acids which are typically used in common carbon nanomaterial functionalization procedures. The MWCNTs are functionalized in one pot using a free radical grafting reaction. The clove-functionalized MWCNTs (CMWCNTs) are then dispersed in distilled water (DI water), producing a highly stable CMWCNT aqueous suspension. The CMWCNTs are characterized using Raman spectroscopy, X-ray photoelectron spectroscopy and transmission electron microscopy. The electrostatic interactions between the CMWCNT colloidal particles in DI water are verified via zeta potential measurements. UV-vis spectroscopy is also used to examine the stability of the CMWCNTs in the base fluid. The thermo-physical properties of the CMWCNT nano-fluids are examined experimentally and indeed, this nano-fluid shows remarkably improved thermo-physical properties, indicating its superb potential for various thermal applications.
The inhibitory effect of two Schiff bases 3-(5-methoxy-2-hydroxybenzylideneamino)-2-(-5-methoxy-2-hydroxyphenyl)-2,3-dihydroquinazoline-4(1H)-one (MMDQ), and 3-(5-nitro-2-hydroxybenzylideneamino)-2(5-nitro-2-hydroxyphenyl)-2,3-dihydroquinazoline-4(1H)-one (NNDQ) on the corrosion of mild steel in 1M hydrochloric acid were studied using mass loss, potentiodynamic polarization technique and electrochemical impedance spectroscopy measurements at ambient temperature. The investigation results indicate that the Schiff Bases compounds with an average efficiency of 92% at 1.0mM of additive concentration have fairly effective inhibiting properties for mild steel in hydrochloric acid, and acts as mixed type inhibitor character. The inhibition efficiencies measured by all measurements show that the inhibition efficiencies increase with increase in inhibitor concentration. This reveals that the inhibitive mechanism of inhibitors were primarily due to adsorption on mild steel surface, and follow Langmuir adsorption isotherm. The temperature effect on the inhibition process in 1MHCl with the addition of investigated Schiff bases was studied at a temperature range of 30-60°C, and the activation parameters (Ea, ΔH and ΔS) were calculated to elaborate the corrosion mechanism. The differences in efficiency for two investigated inhibitors are associated with their chemical structures.
Zero-dimensional graphene quantum dots (GQDs) consist of single- or few-layer graphene with a size less than 20 nm and stand for a new type of QDs with unique properties combining the graphene nature and size-resulted quantum effects. GQDs possess unique optical and electronic properties, and in particular possess a band-gap less than 2.0 eV because of quantum confinement and edge effects. In this study, we investigated the performance of DSSCs using different thicknesses of ZnO nanoparticles as a photo-anode and GQDs as a green photosensitizer. The current voltage (I-V) test results indicate that the performance of DSSCs is improved by increasing the thickness of the photo-anode and the thickness of 40 μm shows the highest efficiency for DSSC device based on ZnO nanoparticles photo-anodes. The DSSC using ZnO nanoparticles as a photo-anode with thickness of 40 μm shows almost same efficiency when we replaced N-719 with GQDs which is confirmed that using GQDs as an alternative to ruthenium based dyes is a new approach for DSSCs.
Silica supported iron catalyst was prepared from rice husk ash (RHA) via the sol-gel technique using an aqueous solution of iron(III) salt in 3.0 M HNO3. The sample was dried at 110 degrees C and labeled as RHA-Fe. A sample of RHA-Fe was calcined at 700 degrees C for 5 h and labeled as RHA-Fe700. X-ray diffraction spectrogram showed that both RHA-Fe and RHA-Fe700 were amorphous. The SEM/EDX results showed that the metal was present as agglomerates and the Fe ions were not homogeneously distributed in RHA-Fe but RHA-Fe700 was shown to be homogeneous. The specific surface areas for RHA-Fe and RHA-Fe700 were determined by BET nitrogen adsorption studies and found to be 87.4 and 55.8 m(2) g(-1), respectively. Both catalysts showed high activity in the reaction between toluene and benzyl chloride. The mono-substituted benzyltoluene was the major product and both catalysts yielded more than 92% of the product. The GC showed that both the ortho- and para-substituted monoisomers were present in about equal quantities. The minor products consisting of 16 di-substituted isomers were also observed in the GC-MS spectra of both catalytic products. The catalyst was found to be reusable without loss of activity and with no leaching of the metal.
The present study reports the removal of Bisphenol A (BPA) and Ibuprofen (IBP) using adsorbents prepared from batik sludge. The calcite sludge-aluminum hydroxide (CAl) adsorbent was prepared by calcination and followed by aluminum hydroxide impregnation. The batik sludge and prepared adsorbents were characterized by FESEM, TGA, XRD, FTIR and BET techniques. The maximum adsorption capacity, adsorption time, different initial solution pH, ionic strength and regeneration study of the adsorbents were also investigated. Furthermore, the sorption behavior of the pollutants were studied by the Langmuir and Freundlich isotherms. The deposition of Al(OH)3 enhanced the BPA and IBP adsorption capacity on the CAl surface. The maximum removal capacity of BPA and Ibuprofen were 83.53 mg g-1 and 34.96 mg g-1 for the CAl adsorbent. In addition, the kinetic data for BPA and IBP were fitted to the pseudo first order, pseudo second order, Elovich, parabolic diffusion and power function equations to understand the sorption behavior. The adsorption behavior of BPA and IBP was mainly chemisorption. This study shows that CAl is a promising adsorbent for the removal of BPA and IBP.
Graphene oxide (GO) has gained popularity in scientific research and industry due to its superior properties, which can be controlled by the synthesis method and graphite feedstock. Despite the availability of different graphite sources, most of the reported studies used natural graphite flake (NGF) as a source of oxidation for GO synthesis. The effect of various alternative graphite feedstocks on the GO properties has not been investigated systematically. This study investigated the influence of graphite feedstock (natural and synthetic) on the characteristics and properties of GO via modified Hummer's method. Natural graphite flake (NGF), natural graphite powder (NGP), and synthetic graphite powder (SGP) were used as graphite feedstock in the study. Energy-dispersive X-ray analysis revealed that the GO produced using NGP (NGP-GO) has higher oxygen to carbon ratio in comparison to GO made from NGF (NGF-GO) and GO made from SGP (SGP-GO) (35.4, 32.7, and 32.2%, respectively), indicating higher oxidation degree for NGP-GO. Zeta potential analysis for NGP-GO, NGF-GO and SGP-GO were -47.8, -42.6 and -39.4 mV, respectively. Morphological analysis revealed that the structures of GO varied according to graphite feedstock, in which (NGP-GO) and (NGF-GO) were highly exfoliated (single-layered structure) while (SGP-GO) showed a multi-layered structure. Further testing was conducted by decorating silver (Ag) nanoparticles on the GO. The results showed that Ag could be uniformly decorated (no agglomeration) on the surface of GO-NGP, due to the presence of more functional groups. Subsequently, the antimicrobial property of Ag-NGP was the highest with an inhibition diameter of 14.7 ± 1.2 mm (30% higher than the other samples). In conclusion, the properties of GO can be tuned by selecting the suitable graphite feedstock and this might pave the way to new developments in the GO-based applications.
Thermal decomposition of co-precipitated Ni-Fe-HT materials led to the formation a mesoporous Ni-Fe-HT catalyst and we have demonstrated here its active role as solid and active catalyst for the Knoevenagel condensation reaction of various aldehydes with active methylene compounds (R-CH2-CN, where R=CN or CO2Et). High product yields are obtained at moderate temperature under solvent-free conditions and the catalyst can be easily separated from the reaction mixture, simply by filtration and reused several times without a significant loss of its activity. Since these mesoporous metal oxides derived from the NiFe hydrotalcites, their basicity mediated abstraction of the acidic protons from the active methylene compounds was responsible for their catalytic activity under solvent-free conditions.
A liquid crystal physical gel was prepared by the self-assembly of cholesteryl stearate in a nematic liquid crystal, 4-cyano-4'-pentylbiphenyl. The electro-optical properties were tuned by varying the gelator concentration and the gelation conditions. Polarized optical microscopy revealed that cholesteric cholesteryl stearate induced chiral nematic phase in 4-cyano-4'-pentylbiphenyl during the gelation process. As a result, a plate-like gel structure consisting of spherical micropores was formed, as observed by scanning electron microscopy. Electron spin resonance spectroscopy showed that the liquid crystal director orientations in these macrophase-separated structures were massively randomised. For these reasons, the liquid crystal physical gel generated a strong light scattering effect. For 48.0wt% cholesteryl stearate gelled 4-cyano-4'-pentylbiphenyl, the turbid appearance could be switched to a transparent state using a 5.0V alternating current. The response time was about 3.7μs. This liquid crystal physical gel has potential for use in light scattering electro-optical displays.
Superior sensitivity towards H2 gas was successfully achieved with Pt-decorated GaN nanowires (NWs) gas sensor. GaN NWs were fabricated via chemical vapor deposition (CVD) route. Morphology (field emission scanning electron microscopy and transmission electron microscopy) and crystal structure (high resolution X-ray diffraction) characterizations of the as-synthesized nanostructures demonstrated the formation of GaN NWs having a wurtzite structure, zigzaged shape and an average diameter of 30-166nm. The Pt-decorated GaN NWs sensor shows a high response of 250-2650% upon exposure to H2 gas concentration from 7 to 1000ppm respectively at room temperature (RT), and then increases to about 650-4100% when increasing the operating temperature up to 75°C. The gas-sensing measurements indicated that the Pt-decorated GaN NWs based sensor exhibited efficient detection of H2 at low concentration with excellent sensitivity, repeatability, and free hysteresis phenomena over a period of time of 100min. The large surface-to-volume ratio of GaN NWs and the catalytic activity of Pt metal are the most influential factors leading to the enhancement of H2 gas-sensing performances through the improvement of the interaction between the target molecules (H2) and the sensing NWs surface. The attractive low-cost, low power consumption and high-performance of the resultant decorated GaN NWs gas sensor assure their uppermost potential for H2 gas sensor working at low operating temperature.
Grafting of free maleimide and epoxide pendant groups onto the surface of approximately 7-nm silica nanoparticles was investigated. Glycidyloxypropyl groups (3-glycidyloxypropyltrimethoxysilane and 3-aminopropyltrimethoxysilane) that carried epoxide groups and aminopropyl groups were grafted to the silica surface with the help of condensation reactions. Maleimide groups [1,1(')-(methylenedi-4,1-phenelene) bismaleimide] were introduced to the silica surface via nucleophilic addition reaction with the aminopropyl groups pre-grafted onto the surface. The grafted silica samples were characterized using CHN, FTIR, DSC, TGA-FTIR, and 13C and 29Si CP/MAS NMR spectroscopy. NMR analyses revealed that all the functional groups were covalently bonded to the silica surface and most of the maleimide and epoxide rings remained intact on surface. DSC analysis showed that the epoxide groups were more reactive than the maleimide groups.
Herein this research, a visible light active tungsten oxide/copper manganate (WO3/CuMnO2) p-n heterojunction nanocomposite was prepared and has been applied for a signal on photoelectrochemical sensing of antibiotic nitrofurazone (NFZ). Firstly, the n-WO3 nanotiles were synthesized from the cetrimonium bromide (CTAB) assisted hydrothermal method and the p-CuMnO2 nanoparticles were synthesized by using the ultrasound-assisted hydrothermal method. The photoelectrochemical NFZ sensing performance of WO3/CuMnO2 nanocomposite was 1.9 times higher than that of as-synthesized pure WO3 nanotiles. The resulting higher photoelectrochemical performance of the nanocomposite is due to more visible light absorption ability and synergy from p-n heterojunction formation. The designed WO3/CuMnO2 nanocomposite sensor gives satisfactory photocurrent signals for the detection of NFZ in the range of 0.015-32 μM with the detection limit (LOD) of 1.19 nM. The practical applicability of the nanocomposite sensor was monitored in pork liver and tap water samples.