Neodymium-doped polyaniline supported Zn-Al layered double hydroxide (PANI@Nd-LDH) nanocomposite has been prepared via an ex-situ oxidative polymerization process. The as-prepared nanocomposite shows selective fluorescence detection and adsorption of hexavalent chromium Cr(VI) within a short period. The fluorescence intensity of PANI@Nd-LDH decreases linearly with Cr(VI) concentrations ranging from 200 ppb to 1000 ppb with a limit of detection (LOD) of 1.5 nM and a limit of quantification (LOQ) of 96 nM. The sensing mechanism can be ascribed by the inner filter effect of Cr(VI), the intercalation of Cr(VI) within the intergallery region of LDH, and the synergistic affinity of metal ions along with the polymer chain for Cr(VI). The adsorption performance of PANI@Nd-LDH nanocomposite is evaluated for Cr(VI) from wastewaters, which displayed high removal capacity towards Cr(VI) (219 mg/g) as compared on bare Nd-LDH (123 mg/g) and LDH (88 mg/g) respectively. The adsorption of Cr(VI) on PANI@Nd-LDH depends on the pH of the aqueous solution. The adsorption isotherm and kinetics are supported by the Langmuir model and pseudo-second-order model, respectively. Owing to the highly sensitive detection and adsorption of Cr(VI) from aqueous water samples demonstrated the potential application of PANI@Nd-LDH as an excellent environmental probe can be exploited.
The recovery of uranium from non-conventional sources has its importance in the security of nuclear fuel supply as well as producing a more value-added product to the contaminated source. In this paper, uranium is recovered both by developing a hydrothermal process as well as using the removal method. Developing hydrothermal process involves using high uranium concentrated starting material such as xenotime and thorium hydroxide waste produced from the monazite cracking process. Oxalate separation enable to produce a better uranium and thorium separation from the yttrium in xenotime as compared to the hydroxide precipitation. Also, a solvent extraction stage was included to separate the uranium from the thorium in the process using thorium hydroxide waste. The removal method involves using selective leaching for minerals with lower uranium content such as zircon. A better removal for uranium and thorium in zircon is achieved when a heat treatment process was done prior to the leaching stage. White zircon mineral was produced after this treatment and its quality meets the requirement for white ceramic opacifier and glaze.
Organostannum(IV) complexes derived from dicarboxylic acids have been successfully synthesised from triphenylstannum(IV) hydroxide (Ph3SnOH). The complexes were obtained by refluxing Ph3SnOH and the respective dicarboxylic acids (malonic, succinic, glutaric and adipic acids) using a Dean and Stark apparatus in the appropriate solvent. The free ligands and complexes were characterised by C, Hand Sn elemental analysis and spectroscopic methods such as infrared and nuclear magnetic resonance (1H, 13C NMR). Structure determination of triphenylstannum(IV) succinate, 2, showed that each dicarboxylate anion was bonded monodentatically to two triphenylstannum(IV) moieties. The geometry surrounding each stannum atom is close to a tetrahedron. Spectroscopic data obtained for all complexes were found to be similar and thus it may be concluded that all complexes have the same structure as 2.
An attempt has been made in this review to provide some insights into the possible adsorption mechanisms of hexavalent chromium onto layered double hydroxides-based adsorbents by critically examining the past and present literature. Layered double hydroxides (LDH) nanomaterials are typical dual-electronic adsorbents because they exhibit positively charged external surfaces and abundant interlayer anions. A high positive zeta potential value indicates that LDH has a high affinity to Cr(VI) anions in solution through electrostatic attraction. The host interlayer anions (i.e., Cl-, NO3-, SO42-, and CO32-) provide a high anion exchange capacity (53-520 meq/100 g) which is expected to have an excellent exchangeable capacity to Cr(VI) oxyanions in water. Regarding the adsorption-coupled reduction mechanism, when Cr(VI) anions make contact with the electron-donor groups in the LDH, they are partly reduced to Cr(III) cations. The reduced Cr(III) cations are then adsorbed by LDH via numerous interactions, such as isomorphic substitution and complexation. Nonetheless, the adsorption-coupled reduction mechanism is greatly dependent on: (1) the nature of divalent and trivalent salts utilized in LDH preparation, and the types of interlayer anions (i.e., guest intercalated organic anions), and (3) the adsorption experiment conditions. The low Brunauer-Emmett-Teller specific surface area of LDH (1.80-179 m2/g) suggests that pore filling played an insignificant role in Cr(VI) adsorption. The Langmuir maximum adsorption capacity of LDH (Qomax) toward Cr(VI) was significantly affected by the natures of used inorganic salts and synthetic methods of LDH. The Qomax values range from 16.3 mg/g to 726 mg/g. Almost all adsorption processes of Cr(VI) by LDH-based adsorbent occur spontaneously (ΔG° <0) and endothermically (ΔH° >0) and increase the randomness (ΔS° >0) in the system. Thus, LDH has much potential as a promising material that can effectively remove anion pollutants, especially Cr(VI) anions in industrial wastewater.
A layered nanoreactor (zinc hydroxide gallate/nitrate nanohybrid) has been designed as a nano-vessel to confine the gallate/nitrate reaction inside zinc hydroxide layers for production of metal/nitrogen-doped carbon catalysts. Metals (Fe2+, Co2+ and Ni2+) doped and bare zinc hydroxide nitrates (ZHN) were synthesized as the α-phase hydroxide hosts. By an incomplete ion-exchange process, nitrate anions between the layers of the hosts were then partially replaced by the gallate anions to produce the layered nanoreactors. Under heat-treatment, the reaction between the remaining un-exchanged nitrate anions and the organic moiety inside the basal spacing of each nanohybrid plate resulted in obtaining highly porous 3D metal/nitrogen-doped carbon nanosheets. These catalysts were then used as extremely efficient electrocatalysts for catalyzing oxygen reduction reaction (ORR). This study is intended to show the way to get maximum electrocatalytic activity of the metal/N-doped carbon catalysts toward the ORR. This exceptionally high ORR performance originates from the increased available surface, the best pore size range and the uniform distribution of the active sites in the produced catalysts, all provided by the use of new idea of the layered nanoreactor.
Multi-walled carbon nanotubes (MWCNTs) were prepared via chemical vapor deposition (CVD) using a series of different catalysts, derived from FeCoNiAl, CoNiAl and FeNiAl layered double hydroxides (LDHs). Catalyst-active particles were obtained by calcination of LDHs at 800 °C for 5 h. Nitrogen and hexane were used as the carrier gas and carbon source respectively, for preparation of MWCNTs using CVD methods at 800 °C. MWCNTs were allowed to grow for 30 min on the catalyst spread on an alumina boat in a quartz tube. The materials were subsequently characterized through X-ray diffraction, Fourier transform infrared spectroscopy, surface area analysis, field emission scanning electron microscopy and transmission electron microscopy. It was determined that size and yield of MWCNTs varied depending on the type of LDH catalyst precursor that is used during synthesis. MWCNTs obtained using CoNiAl-LDH as the catalyst precursor showed smaller diameter and higher yield compared to FeCoNiAl and FeNiAl LDHs.
Steam explosion of oil palm frond has been carried out under different temperatures between 180 and 210°C for 4 min (severity of 2.96-3.84) after impregnation of the frond chips with water or KOH solution. The effects of impregnation and steam explosion conditions of oil palm fronds on the water soluble fraction and insoluble fraction were investigated. The maximum yield of hemicelluloses in water soluble fractions recovered was 23.49% and 25.33% for water and KOH impregnation, treated with steam explosion at temperature of 210°C (severity of 3.84) with a fractionation efficiency of 77.30% and 83.32%, respectively. Under this condition, the water insoluble fractions contained celluloses at 60.83% and 64.80% for water and KOH impregnation, respectively. The steam explosion temperature of 210°C for 4 min (logR(o) 3.84) was found to be the best condition in the extraction of hemicelluloses from OPF for both types of impregnation.
The preparation of chars and activated carbon as low-cost elemental mercury adsorbents was carried out through the carbonisation of coconut husk (pith and fibre) and the activation of chars with potassium hydroxide (KOH), respectively. The synthesised adsorbents were characterised by using scanning electron microscopy, Fourier transform infrared spectroscopy and nitrogen adsorption/desorption analysis. The elemental mercury removal performance was measured using a conventional flow type packed-bed adsorber. The physical and chemical properties of the adsorbents changed as a result of the carbonisation and activation process, hence affecting on the extent of elemental mercury adsorption. The highest elemental mercury (Hg°) adsorption capacity was obtained for the CP-CHAR (3142.57 µg g(-1)), which significantly outperformed the pristine and activated carbon adsorbents, as well as higher than some adsorbents reported in the literature.
Rice husk (RH), an abundant by-product of rice milling, was used for the preparation of activated carbon (RHAC) via KOH and K(2)CO(3) chemical activation. The activation process was performed at the microwave input power of 600 W for 7 min. RHACs were characterized by low temperature nitrogen adsorption/desorption, scanning electron microscopy and Fourier transform infrared spectroscopy. The adsorption behavior was examined using methylene blue as adsorbate. The K(2)CO(3)-activated sample showed higher yield and better pore structures and adsorption capacity development than the KOH-activated sample, with a BET surface area, total pore volume and monolayer adsorption capacity of 1165 m(2)/g, 0.78 cm(3)/g and 441.52 mg/g, respectively. The results revealed the feasibility of microwave heating for preparation of high surface area activated carbons from rice husks via K(2)CO(3) activation.
Fatty acid methyl ester was produced from used vegetable cooking oil using Mg(1-)(x) Zn(1+)(x)O(2) solid catalyst and the performance monitored in terms of ester content obtained. Used vegetable cooking oil was employed to reduce operation cost of biodiesel. The significant operating parameters which affect the overall yield of the process were studied. The highest ester content, 80%, was achieved with the catalyst during 4h 15 min reaction at 188°C with methanol to oil ratio of 9:1 and catalyst loading of 2.55 wt% oil. Also, transesterification of virgin oil gave higher yield with the heterogeneous catalyst and showed high selectivity towards ester production. The used vegetable cooking oil did not require any rigorous pretreatment. Catalyst stability was examined and there was no leaching of the active components, and its performance was as good at the fourth as at the first cycle.
In this study, a novel continuous reactor has been developed to produce high quality methyl esters (biodiesel) from palm oil. A microporous TiO2/Al2O3 membrane was packed with potassium hydroxide catalyst supported on palm shell activated carbon. The central composite design (CCD) of response surface methodology (RSM) was employed to investigate the effects of reaction temperature, catalyst amount and cross flow circulation velocity on the production of biodiesel in the packed bed membrane reactor. The highest conversion of palm oil to biodiesel in the reactor was obtained at 70 °C employing 157.04 g catalyst per unit volume of the reactor and 0.21 cm/s cross flow circulation velocity. The physical and chemical properties of the produced biodiesel were determined and compared with the standard specifications. High quality palm oil biodiesel was produced by combination of heterogeneous alkali transesterification and separation processes in the packed bed membrane reactor.
In this study, solidification/stabilization (S/S) of nickel hydroxide sludge using ordinary Portland cement (OPC) and oil palm ash (OPA) was carried out. The effects of increased substitution of OPA wt% in the S/S mix designs on the treated samples' physical and chemical characteristics were investigated. The physical characteristics studied were unconfined compressive strength (UCS) and changes in crystalline phases while chemical characteristics studied were leachability of nickel and leachate pH. Results indicated the optimum mix design for S/S of nickel hydroxide sludge using both OPC and OPA at B/S(d)=1 in terms of cost-effectiveness and treatment efficiency was 15 wt% OPA, 35 wt% OPC and 50 wt% sludge. The sufficient UCS and low leached nickel concentrations shown for this mix design indicate the viability of using OPA as substitute of OPC as it can significantly reduce cost normally incurred by usage of high amounts of OPC.
Activated carbon was prepared from coconut husk using physicochemical activation method which consisted of potassium hydroxide (KOH) treatment and carbon dioxide (CO(2)) gasification. The effects of three preparation variables (CO(2) activation temperature, CO(2) activation time and KOH:char impregnation ratio) on the 2,4,6-trichlorophenol (2,4,6-TCP) uptake and activated carbon yield were investigated. Based on the central composite design, two quadratic models were developed to correlate the preparation variables to the two responses. From the analysis of variance (ANOVA), the most influential factor on each experimental design response was identified. The activated carbon preparation conditions were optimized by maximizing both the 2,4,6-TCP uptake and activated carbon yield. The predicted 2,4,6-TCP uptake and carbon yield from the models agreed satisfactorily with the experimental values. The optimum conditions for preparing activated carbon from coconut husk for adsorption of 2,4,6-TCP were found as follow: CO(2) activation temperature of 750 degrees C, CO(2) activation time of 2.29 h and KOH:char impregnation ratio of 2.91, which resulted in 191.73 mg/g of 2,4,6-TCP uptake and 20.16 % of activated carbon yield.
The aim of this work was to study radiation and the effects of temperature on conductivity properties of polyvinyl alcohol (PVA)-based potassium hydroxide (KOH) and propylene carbonate (PC), where the ionic conduction preferentially occurs in the amorphous phase by free radicals ions through gamma-irradiation. Alkaline composite polymer electrolyte (ACPE) consisting of PVA, KOH and PC of different concentration ratios were prepared by solvent-casting technique. The ACPE were irradiated with different doses from 5 kGy up to 200 kGy. The conductivity properties of the electrolyte films were measured at different frequencies in the range 20 Hz to 1 MHz using LCR meter. The results showed that the conductivity properties were dependent on the radiation dose, temperature and the concentration of the polymer blends.
In this work, preparation of granular activated carbon from oil palm biodiesel solid residue, oil palm shell (PSAC) by microwave assisted KOH activation has been attempted. The physical and chemical properties of PSAC were characterized using scanning electron microscopy, volumetric adsorption analyzer and elemental analysis. The adsorption behavior was examined by performing batch adsorption experiments using methylene blue as dye model compound. Equilibrium data were simulated using the Langmuir, Freundlich and Temkin isotherm models. Kinetic modeling was fitted to the pseudo-first-order, pseudo-second-order and Elovich kinetic models, while the adsorption mechanism was determined using the intraparticle diffusion and Boyd equations. The result was satisfactory fitted to the Langmuir isotherm model with a monolayer adsorption capacity of 343.94mg/g at 30°C. The findings support the potential of oil palm shell for preparation of high surface area activated carbon by microwave assisted KOH activation.
Layered double hydroxide of Mg-Al-carbonate system (MACH) was prepared and its heat-treated product (MACHT) was obtained by calcination at 500 degrees C. The resulting materials were used as an adsorbent for removal of color from synthetic textile wastewater (STW) and textile wastewater (TWW). Batch kinetic study showed that these materials are an efficient adsorbent for textile dye. The maximum adsorption capacities between 16 to 32 mg of dyes per g of adsorbent was obtained by fitting the adsorption data to the Langmuir adsorption Isotherm. It was found that the adsorption capacity of MACHT is higher than MACH.
Hybridization of beneficial organic guest with inorganic host affords scientists an opportunity to synthesize various combinations of new organic-inorganic nanohybrids with various potential applications, especially for controlled delivery of beneficial agent and storage. A new layered organic-inorganic nanohybrid material containing an agrochemical, 4-(2,4-dichlorophenoxy)butyrate (DPBA) in Zn-Al-layered double hydroxide inorganic interlayer was synthesised by direct and indirect methods. Both methods yielded mesoporous-type, phase pure, well-ordered layered nanohybrids with similar basal spacing of 28.5-28.7 angstroms and organic loading of around 54.3%. Compared to the material prepared by direct method, the ion exchanged product inherited more of the host's properties especially the pore structure and the organic moiety is also more easily released. This shows that the method of preparation plays an important role in determining the resulting physicochemical properties, in particular the release property and therefore can be used as a means to tune up the release property of the beneficial agent.
Metanilate-layered double hydroxide nanohybrid compound was synthesized for controlled release purposes through co-precipitation method of the metal cations and organic anion. The effect of various divalent metal cations (M2+), namely Zn2+, Mg2+ and Ca2+ on the formation of metanilate-LDH nanohybrids, in which metanilate anion was intercalated into three different layered double hydroxide (LDH) systems; Zn-Al, Mg-Al and Ca-Al were investigated. The syntheses were carried out with M2+ to Al3+ initial molar ratio, R of 4. The pH of the mother liquor was maintained at pH 7.5 and 10 during the synthesis, and the resulting mixture was aged at around 70 degrees C for about 18 h. The intercalation of metanilate anion into the host was found to be strongly influenced by the M2+ that formed the inorganic metal hydroxide layers. Under our experimental condition, the formation of the nanohybrid materials was found to be more feasible for the Zn-Al than for the other two systems, in which the former showed well-ordered layered organic-inorganic nanohybrid structure with good crystallinity. Intercalation is confirmed by the expansion of the interlayer spacing to about 15-17 A when metanilate was introduced into the interlamellae of Zn-Al LDHs. In addition, CHNS and FTIR analyses also support that metanilate anion has been successfully intercalated into the interlamellae of the inorganic LDH. Apart from M2+, this study also shows that the initial pH of the mother liquor plays an important role in determining the physicochemical properties of the resulting nanohybrids, especially the mole fraction of the Zn2+ substituted by the Al3+ ion in the LDH inorganic sheets which in turn controlled the loading percentage of the organic anion, surface properties and the true density. Preliminary study shows that LDH can be used to host beneficial guests, active agent with controlled release capability of the guests. Generally the overall process is governed by pseudo second order kinetic but for the first 180 min, the release process can be slightly better described by parabolic diffusion than the other models.
Layered organic-inorganic hybrid nanocomposite material was synthesised using 4-chlorophenoxyacetate (4CPA) as guest anion intercalated into the Zn-Al layered double hydroxide inorganic host by direct co-precipitation method at pH = 7.5 and Zn to Al molar ratio of 4. Both PXRD and FTIR results confirmed that the 4CPA was successfully intercalated into the Zn-AI-LDH interlayer. As a result, a well-ordered nanolayered organic-inorganic hybrid nanocomposite, with the expansion of the basal spacing from 8.9 angstroms in the layered double hydroxide to 20.1 angstroms in the resulting nanocomposite was observed. The FTIR spectrum of the nanocomposite (ZAC) showed that it composed spectral features of Zn-AI-LDH (ZAL) and 4CPA. The nanocomposites synthesized in this work are of mesoporous-type containing 39.8% (w/w) of 4CPA with mole fraction of Al3+ in the inorganic brucite-like layers (xAI) of 0.224. The release studies showed a rapid release of the 4CPA for the first 600 min, and more sustained thereafter. The total amount of 4CPA released from the nanocomposite interlayer into the aqueous solution were 21%, 66%, and 72% in 0.0001, 0.00025, and 0.0005 M sodium carbonate, respectively. In distilled water, about 75, 35, and 57% of 4CPA could be released in 1000 min, when the pH of the release media was set at 3, 6.25, and 12, respectively. In comparison with a structurally similar organic moiety with one more chlorine atom at the 2-position of the aromatic ring, namely 2,4-dichlorophenoxyacetate (24D), the 4CPA showed a slower release rate. The slightly bulkier organic moiety of 24D together with the presence of chlorine atom at the 2-position presumably had contributed to its higher release rate, and it seems that these factors may be exploited for tuning the release rate of intercalated guest anions with similar properties. This study suggests that layered double hydroxide can be used as a carrier for an active agent and the chemical structure of the intercalated moiety can be used to tune the desired release kinetics of the beneficial agent.
A label-free chemical bonding strategy mediated by reduced graphene oxide (rGO) basal plane functional groups has been developed for cardiac Troponin I (cTnI) detection. Four different chemical strategies on respective electrode sensing surface were precedingly examined using electrochemical impedance spectroscopy. The impedimetric assessment was carried out by sweeping frequency at the range 0.1-500 kHz perturbated at a small amplitude of AC voltage (25 mV). The chemical strategy-4 denoted as S-4 shows a significant analytical performance on cTnI detection in spiked buffer and human serum, whereby the pre-mixture of rGO and (3-Aminopropyl)triethoxysilane (APTES) creates a large number of amine sites (-NH2), which significantly enhanced the antibody immobilization without excessive functionalization. The as-fabricated immunosensor exhibited an ultra-low limit of detection of 6.3 ag mL-1 and the lowest antigen concentration measured was at 10 ag mL-1. The immunosensor showed a linear and wide range of cTnI detection (10 ag mL-1-100 ng mL-1) in human serum with a regression coefficient of 0.9716, rapid detection (5 min of binding time), and stable and highly reproducible bioelectrode response with RSD