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Efficient Removal of Tetracycline and Bisphenol A from Water with a New Hybrid Clay/TiO2 Composite
(2023)
New TiO2 hybrid composites were prepared fromkaolinclay, predried and carbonized biomass, and titanium tetraisopropoxideand explored for tetracycline (TET) and bisphenol A (BPA) removalfrom water. Overall, the removal rate is 84% for TET and 51% for BPA.The maximum adsorption capacities (q (m))are 30 and 23 mg/g for TET and BPA, respectively. These capacitiesare far greater than those obtained for unmodified TiO2. Increasing the ionic strength of the solution does not change theadsorption capacity of the adsorbent. pH changes only slightly changeBPA adsorption, while a pH > 7 significantly reduces the adsorptionof TET on the material. The Brouers-Sotolongo fractal modelbest describes the kinetic data for both TET and BPA adsorption, predictingthat the adsorption process occurs via a complex mechanism involvingvarious forces of attraction. Temkin and Freundlich isotherms, whichbest fit the equilibrium adsorption data for TET and BPA, respectively,suggest that adsorption sites are heterogeneous in nature. Overall,the composite materials are much more effective for TET removal fromaqueous solution than for BPA. This phenomenon is assigned to a differencein the TET/adsorbent interactions vs the BPA/adsorbent interactions:the decisive factor appears to be favorable electrostatic interactionsfor TET yielding a more effective TET removal.
Novel metal-doped bacteriostatic hybrid clay composites for point-of-use disinfection of water
(2017)
This study reports the facile microwave-assisted thermal preparation of novel metal-doped hybrid clay composite adsorbents consisting of Kaolinite clay, Carica papaya seeds and/or plantain peels (Musa paradisiaca) and ZnCl2. Fourier Transformed IR spectroscopy, X-ray diffraction, Scanning Electron Microscopy and Brunauer-Emmett-Teller (BET) analysis are employed to characterize these composite adsorbents. The physicochemical analysis of these composites suggests that they act as bacteriostatic rather than bacteriacidal agents. This bacterostactic action is induced by the ZnO phase in the composites whose amount correlates with the efficacy of the composite. The composite prepared with papaya seeds (PS-HYCA) provides the best disinfection efficacy (when compared with composite prepared with Musa paradisiaca peels-PP-HYCA) against gram-negative enteric bacteria with a breakthrough time of 400 and 700 min for the removal of 1.5 x10(6) cfu/mL S. typhi and V. cholerae from water respectively. At 10(3) cfu/mL of each bacterium in solution, 2 g of both composite adsorbents kept the levels the bacteria in effluent solutions at zero for up to 24 h. Steam regeneration of 2 g of bacteria-loaded Carica papaya prepared composite adsorbent shows a loss of ca. 31% of its capacity even after the 3rd regeneration cycle of 25 h of service time. The composite adsorbent prepared with Carica papaya seeds will be useful for developing simple point-of-use water treatment systems for water disinfection application. This composite adsorbent is comparatively of good performance and shows relatively long hydraulic contact times and is expected to minimize energy intensive traditional treatment processes.
A new micro/mesoporous hybrid clay nanocomposite prepared from kaolinite clay, Carica papaya seeds, and ZnCl2 via calcination in an inert atmosphere is presented. Regardless of the synthesis temperature, the specific surface area of the nanocomposite material is between approximate to 150 and 300 m(2)/g. The material contains both micro- and mesopores in roughly equal amounts. X-ray diffraction, infrared spectroscopy, and solid-state nuclear magnetic resonance spectroscopy suggest the formation of several new bonds in the materials upon reaction of the precursors, thus confirming the formation of a new hybrid material. Thermogravimetric analysis/differential thermal analysis and elemental analysis confirm the presence of carbonaceous matter. The new composite is stable up to 900 degrees C and is an efficient adsorbent for the removal of a water micropollutant, 4-nitrophenol, and a pathogen, E. coli, from an aqueous medium, suggesting applications in water remediation are feasible.
New hybrid clay materials with good affinity for phosphate ions were developed from a combination of biomass-Carica papaya seeds (PS) and Musa paradisiaca (Plantain peels-PP), ZnCl2 and Kaolinite clay to produce iPS-HYCA and iPP-HYCA composite adsorbents respectively. Functionalization of these adsorbents with an organosilane produced NPS-HYCA and NPP-HYCA composite adsorbents. The pH(pzc) for the adsorbents were 7.83, 6.91, 7.66 and 6.55 for iPS-HYCA, NPS-HYCA, iPP-HYCA and NPP-HYCA respectively. Using the Brouer-Sotolongo isotherm model which best predict the adsorption capacity of composites for phosphate, iPP-HYCA, iPS-HYCA, NPP-HYCA, and NPS-HYCA composite adsorbents respectively. When compared with some commercial resins, the amino-functionalized adsorbents had better adsorption capacities. Furthermore, amino-functionalized adsorbents showed improved adsorption capacity and rate of phosphate uptake (as much as 40-fold), as well as retain 94% (for NPS-HYCA) and 84.1% (for NPP-HYCA) efficiency for phosphate adsorption after 5 adsorption-desorption cycles (96 h of adsorption time with 100 mg/L of phosphate ions) as against 37.5% (for iPS-HYCA) and 35% (for iPP-HYCA) under similar conditions. In 25 min desorption of phosphate ion attained equilibrium. These new amino-functionalized hybrid clay composite adsorbents, which were prepared by a simple means that is sustainable, have potentials for the efficient capture of phosphate ions from aqueous solution. They are quickly recovered from aqueous solution, non-biodegradable (unlike many biosorbent) with potentials to replace expensive adsorbents in the future. They have the further advantage of being useful in the recovery of phosphate for use in agriculture which could positively impact the global food security programme. (C) 2017 Elsevier Ltd. All rights reserved.
Visible-Light-Mediated Photodynamic Water Disinfection @ Bimetallic-Doped Hybrid Clay Nanocomposites
(2019)
This study reports a new class of photocatalytic hybrid clay nanocomposites prepared from low-cost sources (kaolinite clay and Carica papaya seeds) doped with Zn and Cu salts via a solvothermal process. X-ray diffraction analysis suggests that Cu-doping and Cu/Zn-doping introduce new phases into the crystalline structure of Kaolinite clay, which is linked to the reduced band gap of kaolinite from typically between 4.9 and 8.2 eV to 2.69 eV for Cu-doped and 1.5 eV for Cu/Zn hybrid clay nanocomposites (Nisar, J.; Arhammar, C.; Jamstorp, E.; Ahuja, R. Phys. Rev. B 2011, 84, 075120). In the presence of solar light irradiation, Cu- and Cu/Zn-doped nanocomposites facilitate the electron hole pair separation. This promotes the generation of singlet oxygen which in turn improves the water disinfection efficiencies of these novel nanocomposite materials. The nanocomposite materials were further characterized using high-resolution scanning electron microscopy, fluorimetry, therrnogravimetric analysis, and Raman spectroscopy. The breakthrough times of the nanocomposites for a fixed bed mode of disinfection of water contaminated with 2.32 x 10(7) cfu/mL E. coli ATCC 25922 under solar light irradiation are 25 h for Zn-doped, 30 h for Cu-doped, and 35 h for Cu/Zn-doped nanocomposites. In the presence of multidrug and multimetal resistant strains of E. coli, the breakthrough time decreases significantly. Zn-only doped nanocomposites are not photocatalytically active. In the absence of light, the nanocomposites are still effective in decontaminating water, although less efficient than under solar light irradiation. Electrostatic interaction, metal toxicity, and release of singlet oxygen (only in the Cu-doped and Cu/Zn-doped nanocomposites) are the three disinfection mechanisms by which these nanocomposites disinfect water. A regrowth study indicates the absence of any living E. coli cells in treated water even after 4 days. These data and the long hydraulic times (under gravity) exhibited by these nanocomposites during photodisinfection of water indicate an unusually high potential of these nanocomposites as efficient, affordable, and sustainable point-of-use systems for the disinfection of water in developing countries.
The competitive extraction of Cr(III) onto Nauclea diderrichii seed epicarp doped with MnO2 nanoparticles (MnO2 nano-bioextractant (MNB)) in a single and binary batch system was studied. For validity of experimental data, chi square test, root mean square error, sum of the square errors, hybrid fractional error function, Marquart’s percent standard deviation and standard absolute error were used. Among the kinetic models used, pseudo-second-order and Langmuir equations gave the best fits for the experimental data, with qe (mg g) for the uptake of Cr(III) in single metal system onto MNB, then Cr(III) with Cd(II), Pb(II), Hg(II), KCl and CaCl2 in binary metal systems onto MNB were 2.611, then 1.989, 1.016, 2.208, 1.249 and 1.868 from kinetic standpoint, respectively. The initial sorption rates, h (mg/g/min), and half lives, t1/2 (min), for the uptake of Cr(III) in single metal system onto MNB, then Cr(III) with Cd(II), Pb(II), Hg(II), KCl and CaCl2 in binary metal system onto MNB were 3.497, then 2.311, 2.274, 0.242, 2.956, 45.568 and 0.747, then 5.769, 1.766, 12.144, 1.762, and 2.415, respectively. Physicochemical surface analyses such as pH of point of zero charge, Brunauer–Emmett–Teller single point and multi-point techniques for surface area analyses, scanning electron microscopy and transmission electron microscopy were done on MNB and MnO2 nanoparticles in order to understand their surface microstructures. Desorption study showed that MNB can be recycled and used for future study. Hence, MNB showed good potential to remediate Cr(III) from wastewaters and polluted water.
Toxic Cr(III) which poses environmental hazard to flora and fauna was efficiently abstracted by low-cost Nauclea diderrichii seed biomass (NDS) with good sequestral capacity for this metal was investigated in this study. The NDS surface analyses showed that it has a specific surface area of 5.36 m(2)/g and pHpzc of 4.90. Thermogravimetric analysis of NDS showed three consecutive weight losses from 50-200 degrees C (ca. 5%), 200-400 C (ca. 35%), >400 degrees C (ca. 10%), corresponding to external water molecules, structural water molecules and heat induced condensation reactions respectively. Differential thermogram of NDS presented a large endothermic peak between 20-510 degrees C suggesting bond breakage and dissociation with the ultimate release of small molecules. The experimental data showed kinetically fast biosorption with increased initial Cr(III) concentrations, indicating the role of external mass transfer mechanism as the rate controlling mechanism in this adsorption process. The Langmuir biosorption capacity of NDS was 483.81 mg/g. The use of the corrected Akaike Information Criterion tool for ranking equilibrium models suggested that the Freundlich model best described the experimental data, which is an indication of the heterogeneous nature of the active sites on the surface of NDS. N. diderrichii seed biomass is an easily sourced, cheap and environmental friendly biosorbent which will serve as a good and cost effective alternative to activated carbon for the treatment of polluted water and industrial effluents. (C) 2012 King Saud University. Production and hosting by Elsevier B.V. All rights reserved.
OPTIMIZATION OF THE BIOSORPTION OF Cr3+, Cd2+ AND Pb2+ USING A NEW BIOWASTE: Zea mays SEED CHAFF
(2016)
This study highlights the potential use of yellow Zea mays seed chaff (YZMSC) biomass as a biosorbent for the removal of Cr3+, Cd2+ and Pb2+ ions from aqueous solutions. Fourier transformed Infrared analysis of the biomass suggests that YZMSC biomass is basically composed of cellulose and methyl cellulose. The biosorption capacities, q(max), of YZMSC biomass for Cr3+, Cd2+ and Pb2+ are 14.68, 121.95 and 384.62 mg/g respectively. Biosorption equilibrium was achieved at 20, 30 and 60 min for Cr3+, Cd2+ and Pb2+ respectively. YZMSC biomass was found to have higher biosorption capacity and overall kinetic rate of uptake for Pb2+ than for Cd2+ and Cr3+. However, Cr3+ had better initial kinetic rate of uptake by the biomass than Pb2+ and Cd2+. The Freundlich equilibrium isotherm model was found to describe equilibrium data better than Langmuir model suggesting that biosorption of these metal ions could be on more than one active site on the surface of YZMSC biomass. Kinetic study predicted the pseudo-second kinetic model as being able to better describe kinetic data obtained than either modified pseudo-first order or Bangham kinetic models. Biosorption of Cr3+, Cd2+ and Pb2+ onto YZMSC biomass was endothermic in nature with large positive entropy values. Biosorption of these metal ions onto YZMSC biomass was observed to be feasible and spontaneous above 283 K. Optimization of biomass weight for the removal of these metal ions suggest that 384 kg, 129 kg and 144 kg of YZMSC biomass is required for the removal of 95% of Cr3+, Cd2+ and Pb2+ metal ions respectively from 100 mg/L of metal ions in 10 tonnes of aqueous solutions.
This study is a first-hand report of the immobilization of Nauclea diderrichii seed waste biomass (ND) (an agro-waste) with eco-friendly mesoporous silica (MS) and graphene oxide-MS (GO+MS ) nanoparticles, producing two new hybrid materials namely: MND adsorbent for agro-waste modified with MS and GND adsorbent for agro-waste modified with GO+MS nanoparticles showed improved surface area, pore size and pore volume over those of the agro-waste. The abstractive potential of the new hybrid materials was explored for uptake of Cr(III) and Pb(II) ions. Analysis of experimental data from these new hybrid materials showed increased initial sorption rate of Cr(III) and Pb(II) ions uptake. The amounts of Cr(III) and Pb(II) ions adsorbed by MND and GND adsorbents were greater than those of ND. Modification of N. diderrichii seed waste significantly improved its rate of adsorption and diffusion coefficient for Cr(III) and Pb(II) more than its adsorption capacity. The rate of adsorption of the heavy metal ions was higher with GO+MS nanoparticles than for other adsorbents. Kinetic data were found to fit well the pseudo-second-order and the diffusion-chemisorption kinetic models suggesting that the adsorption of Cr(III) and Pb(II) onto these adsorbents is mainly through chemisorption mechanism. Analysis of kinetic data with the homogeneous particle diffusion kinetic model suggests that particle diffusion (diffusion of ions through the adsorbent) is the rate-limiting step for the adsorption process.
This study reports the sequestration of Cd(II) and Hg(II) using a new biosorbent. Nauclea diderrichii seed biomass. Experimental data obtained were fitted into kinetic and thermodynamic models. Experimental data fitted best into pseudo-second order kinetic model among others. Results obtained kinetically revealed that the biosorption of Cd(II) and Hg(II) using N. diderrichii seed biosorbent increased with increase in temperature. At the highest temperature, which was 333 K. the highest amount of metal biosorbed, q(e), for Cd(II) and Hg(II) obtained were 6.30 and 6.15 mg/g respectively. The biosorption of Cd(II) was kinetically faster than that of Hg(II), the highest initial biosorption rates for Cd(II) and Hg(II) were 56.19 and 4.39 mg/g min respectively. Thermodynamic parameters obtained by Erying equation from this study revealed that the biosorption process was spontaneous, feasible, endothermic with a decrease in the degree of chaos in the biosorption system. (C) 2012 Elsevier Ltd. All rights reserved.