Carbon nanotubes-mesostructured silica nanoparticles (CNT-MSN) composites were prepared by a simple one step method with various loading of CNT. Their surface properties were characterized by XRD, N2 physisorption, TEM and FTIR, while the adsorption performance of the CNT-MSN composites were evaluated on the adsorption of methylene blue (MB) while varying the pH, adsorbent dosage, initial MB concentration, and temperature. The CNTs were found to improve the physicochemical properties of the MSN and led to an enhanced adsorptivity for MB. N2 physisorption measurements revealed the development of a bimodal pore structure that increased the pore size, pore volume and surface area. Accordingly, 0.05 g L(-1) CNT-MSN was able to adsorb 524 mg g(-1) (qm) of 60 mg L(-1) MB at pH 8 and 303 K. The equilibrium data were evaluated using the Langmuir, Freundlich, Temkin, and Dubinin-Radushkevich isotherm models, with the Langmuir model affording the best fit to the adsorption data. The adsorption kinetics were best described by the pseudo-first order model. These results indicate the potential of CNT-MSN composites as effective new adsorbents for dye adsorption.
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.
The study reports on the preparation of cellulose nanocrystals (CNCs) from wastepaper, as an environmental friendly approach of source material, which can be a high availability and low-cost precursor for cellulose nanomaterial processing. Alkali and bleaching treatments were employed for the extraction of cellulose particles followed by controlled-conditions of acid hydrolysis for the isolation of CNCs. Attenuated total reflectance Fourier Transform Infrared (ATR FTIR) spectroscopy was used to analyze the cellulose particles extracted while Transmission electron microscopy images confirmed the presence of CNCs. The diameters of CNCs are in the range of 3-10nm with a length of 100-300nm while a crystallinity index of 75.9% was determined from X-ray diffraction analysis. The synthesis of this high aspect ratio of CNCs paves the way toward alternative reuse of wastepaper in the production of CNCs.
Electrochemical dechlorination of chlorobenzene in organic solutions was studied. Electrolysis of chlorobenzene in acetonitrile solution in a one-compartment cell fitted with a platinum cathode and a zinc anode at 60mA/cm(2) and 0 degrees C was found to be the optimum conditions, which gave complete dechlorination of chlorobenzene. However, similar result could not be achieved when applying these conditions to 1,3-dichlorobenzene and 1,2,4-trichlorobenzene. We found that the use of naphthalene which reacted as a mediator in the appropriate system could accelerate the reduction and gave complete dechlorination of those chlorobenzenes. Moreover, in the presence of naphthalene the reaction time could be shortened by half compared to dechlorination in the absence of naphthalene.
Copper (Cu, 1-5 wt%) was loaded onto carbon nanotubes (CNTs) by a simple electrochemical method. The physicochemical properties of catalysts (Cu/CNTs) were characterized by using X-ray diffraction (XRD), transmission electron microscopy (TEM), nitrogen (N2) adsorption-desorption, Fourier transform infra-red spectroscopy (FTIR), X-ray photoelectron spectroscopy (XPS), and electron spinning resonance (ESR). The results showed that the Cu was distributed well on the CNT surface by the interaction of Cu(2+) ions with -OH and -COOH groups on the CNT surface, which preferentially occurred at the defect sites along the CNT backbone. The Cu-O-C bonds formed were found to play an important role in enhancing the photoactivity of the catalysts. The highest number of Cu-O-C bonds possessed by 3 wt% Cu/CNTs demonstrated the best performance in the degradation of p-chloroaniline (96%) under UV light irradiation within 5 h of reaction at 27 °C and under neutral pH conditions. Kinetic studies showed that the degradation followed the pseudo-first order model and the surface reaction was the controlling step. It is believed that these results could contribute to the synthesis of various supported catalysts for various applications.
The unique three-dimensional pore structure of KCC-1 has attracted significant attention and has proven to be different compared to other conventional mesoporous silica such as the MCM-41 family, SBA-15, or even MSN nanoparticles. In this research, we carefully examine the morphology of KCC-1 to define more appropriate nomenclature. We also propose a formation mechanism of KCC-1 based on our experimental evidence. Herein, the KCC-1 morphology was interpreted mainly on the basis of compiling all observation and information taken from SEM and TEM images. Further analysis on TEM images was carried out. The gray value intensity profile was derived from TEM images in order to determine the specific pattern of this unique morphology that is found to be clearly different from that of other types of porous spherical-like morphologies. On the basis of these results, the KCC-1 morphology would be more appropriately reclassified as bicontinuous concentric lamellar morphology. Some physical characteristics such as the origin of emulsion, electrical conductivity, and the local structure of water molecules in the KCC-1 emulsion were disclosed to reveal the formation mechanism of KCC-1. The origin of the KCC-1 emulsion was characterized by the observation of the Tyndall effect, conductometry to determine the critical micelle concentration, and Raman spectroscopy. In addition, the morphological evolution study during KCC-1 synthesis completes the portrait of the formation of mesoporous silica KCC-1.
Solid acid catalyzed cracking of waste oil-derived fatty acids is an attractive route to hydrocarbon fuels. HZSM-5 is an effective acid catalyst for fatty acid cracking; however, its microporous nature is susceptible to rapid deactivation by coking. We report the synthesis and application of hierarchical HZSM-5 (h-HZSM-5) in which silanization of pre-crystallized zeolite seeds is employed to introduce mesoporosity during the aggregation of growing crystallites. The resulting h-HZSM-5 comprises a disordered array of fused 10-20 nm crystallites and mesopores with a mean diameter of 13 nm, which maintain the high surface area and acidity of a conventional HZSM-5. Mesopores increase the yield of diesel range hydrocarbons obtained from oleic acid deoxygenation from ~20% to 65%, attributed to improved acid site accessibility within the hierarchical network.
Nickel (Ni), cobalt (Co), and zinc (Zn) loaded on fibrous silica KCC-1 was investigated for CO2 methanation reactions. Ni/KCC-1 exhibits the highest catalyst performance with a CH4 formation rate of 33.02 × 10-2 molCH4 molmetal-1 s-1, 1.77 times higher than that of Co/KCC-1 followed by Zn/KCC-1 and finally the parent KCC-1. A pyrrole adsorption FTIR study reveals shifting of perturbed N-H stretching decreasing slightly with the addition of metal oxide, suggesting that the basic sites of catalyst were inaccessible due to metal oxide deposition. The strengths of basicity were found to follow sthe equence KCC-1, Ni/KCC-1, Zn/KCC-1, and Co/KCC-1. The data were supported by N2 adsorption desorption analysis, where Co/KCC-1 displayed the greatest reduction in total surface area whereas Ni/KCC-1 displayed the least reduction. The elucidation of difference mechanism pathways has also been studied by in situ IR spectroscopy studies to determine the role of different metal oxides in CO2 methanation. It was discovered that Ni/KCC-1 and Co/KCC-1 follow a dissociative mechanism of CO2 methanation in which the CO2 molecule was dissociated on the surface of the metal oxide before migration onto the catalyst surface. This was confirmed by the evolution of a peak corresponding to carbonyl species (COads) on a metal oxide surface in FTIR spectra. Zn/KCC-1, on the other hand, showed no such peak, indicating associative methanation pathways where a hydrogen molecule interacts with an O atom in CO2 to form COads and OH. These results offers a better understanding for catalytic studies, particularly in the field of CO2 recycling.
In this work, mesostructured silica nanoparticles (MSN(AP)) with high adsorptivity were prepared by a modification with 3-aminopropyl triethoxysilane (APTES) as a pore expander. The performance of the MSN(AP) was tested by the adsorption of MB in a batch system under varying pH (2-11), adsorbent dosage (0.1-0.5 g L(-1)), and initial MB concentration (5-60 mg L(-1)). The best conditions were achieved at pH 7 when using 0.1 g L(-1) MSN(AP) and 60 mg L(-1)MB to give a maximum monolayer adsorption capacity of 500.1 mg g(-1) at 303 K. The equilibrium data were evaluated using the Langmuir, Freundlich, Temkin, and Harkins-Jura isotherms and fit well to the Freundlich isotherm model. The adsorption kinetics was best described by the pseudo-second order model. The results indicate the potential for a new use of mesostructured materials as an effective adsorbent for MB.
Fibrous silica-titania (FST) catalysts were synthesized by microemulsion followed by silica seed-crystal crystallization methods under various molar ratios of toluene to water (T/W). The catalysts were characterized by XRD, UV-DRS, FESEM, TEM, AFM, N2 adsorption-desorption, FTIR, and ESR. The results revealed that altering the T/W ratio affected the growth of the silica and titania and led to different size, fiber density, silica-titania structure, and number of hydroxyl groups, as well as oxygen vacancies in the FSTs, which altered their behavior toward subsequent application. Photodegradation of ibuprofen (IBP) are in the following order: FST(6:1) (90%) > FST(5:1) (84%) > FST(7:1) (79%) > commercial TiO2 (67%). A kinetics study using Langmuir-Hinshelwood model illustrated that the photodegradation followed the pseudo-first-order and adsorption was the rate-limiting step. Optimization by response surface methodology (RSM) showed that the pH, initial concentration, and catalyst dosage were the remarkable parameters in photodegradation of IBP. The FST (6:1) maintained its photocatalytic activities for up to five cycles reaction without serious catalyst deactivation, and was also able to degrade other endocrine-disrupting chemicals, indicating its potential use for the treatment of those chemicals in wastewater.
Mesoporous silica nanoparticles (MSNs) were synthesized with variable microwave power in the range of 100-450 W, and the resulting enhancement of MSN crystal growth was evaluated for the adsorption and release of ibuprofen. X-ray diffraction (XRD) revealed that the MSN prepared under the highest microwave power (MSN450) produced the most crystallized and prominent mesoporous structure. Enhancement of the crystal growth improved the hexagonal order and range of silica, which led to greater surface area, pore width and pore volume. MSN450 exhibited higher ibuprofen adsorption (98.3 mg/g), followed by MSN300(81.3 mg/g) and MSN100(74.1 mg/g), confirming that more crystallized MSN demonstrated higher adsorptivity toward ibuprofen. Significantly, MSN450 also contained more hydroxyl groups that provided more adsorption sites. In addition, MSN450 exhibited comparable ibuprofen adsorption with conventionally synthesized MSN, indicating the potential of microwave treatment in the synthesis of related porous materials. In vitro drug release was also investigated with simulated biological fluids and the kinetics was studied under different pH conditions. MSN450 showed the slowest release rate of ibuprofen, followed by MSN300 and MSN100. This was due to the wide pore diameter and longer range of silica order of the MSN450. Ibuprofen release from MSN450 at pH 5 and 7 was found to obey a zero-order kinetic model, while release at pH 2 followed the Kosmeyer-Peppas model.
In this work, two low-cost wastes, bivalve shell (BS) and Zea mays L. husk leaf (ZHL), were investigated to adsorb malachite green (MG) from aqueous solutions. The ZHL was treated with calcined BS to give the BS-ZHL, and its ability to adsorb MG was compared with untreated ZHL, calcined BS and Ca(OH)(2)-treated ZHL under several different conditions: pH (2-8), adsorbent dosage (0.25-2.5 g L(-1)), contact time (10-30 min), initial MG concentration (10-200 mg L(-1)) and temperature (303-323 K). The equilibrium studies indicated that the experimental data were in agreement with the Langmuir isotherm model. The use of 2.5 g L(-1) BS-ZHL resulted in the nearly complete removal of 200 mg L(-1) of MG with a maximum adsorption capacity of 81.5 mg g(-1) after 30 min of contact time at pH 6 and 323 K. The results indicated that the BS-ZHL can be used to effectively remove MG from aqueous media.
In this study, calcined Lapindo volcanic mud (LVM) was used as an adsorbent to remove an anionic dye, methyl orange (MO), from an aqueous solution by the batch adsorption technique. Various conditions were evaluated, including initial dye concentration, adsorbent dosage, contact time, solution pH, and temperature. The adsorption kinetics and equilibrium isotherms of the LVM were studied using pseudo-first-order and -second-order kinetic equations, as well as the Freundlich and Langmuir models. The experimental data obtained with LVM fits best to the Langmuir isotherm model and exhibited a maximum adsorption capacity (q(max)) of 333.3 mg g(-1); the data followed the second-order equation. The intraparticle diffusion studies revealed that the adsorption rates were not controlled only by the diffusion step. The thermodynamic parameters, such as the changes in enthalpy, entropy, and Gibbs free energy, showed that the adsorption is endothermic, random and spontaneous at high temperature. The results indicate that LVM adsorbs MO efficiently and could be utilized as a low-cost alternative adsorbent for the removal of anionic dyes in wastewater treatment.
Electrochemical dechlorination of chlorobenzenes in the presence of various arene mediators such as naphthalene, biphenyl, phenanthrene, anthracene, and pyrene, was studied. The amount of mediator required was able to be reduced to 0.01 equiv. for all mediators except for anthracene, with the complete dechlorination of mono-, 1,3-di- and 1,2,4-trichlorobenzene still achieved. This catalytic amount of mediator plays an important role in accelerating the dechlorination through the rapid formation of radical anions prior to reduction of the chlorobenzenes.