Polymeric vanadium pentoxide gel was formed via the reaction of V2O5 powder with hydrogen peroxide. The polymeric vanadium pentoxide gel was then dispersed in alumina gel. Different vanadium loading composites were coated on alumina support and calcined at 500 degrees C for 1 hr. These composite layers were characterized using TGA, FT-IR, XRD, SEM, and Autosorb. It was found that the lamellar structure of polymerized vanadium pentoxide was retained in the inorganic matrix. Crystalline alumina in gamma phase was formed after calcinations. However, the vanadium-alumina mixed oxides are lack of the well defined PXRD peaks for polycrystalline V2O5. This is possibly because the vanadia species are highly dispersed in the alumina matrix or the vanadia species are dispersed as crystalline which is smaller than 4 nm. In addition, the imbedded polymeric vanadium oxide improved the specific area and average pore diameter of the composite layer.
In the present work, palm kernel shell (PKS) biomass waste has been used as a low-cost and easily available precursor to prepare carbon dots (CDs) via microwave irradiation method. The impacts of the reacting medium: water and diethylene glycol (DEG), and irradiation period, as well as the presence of chitosan on the CDs properties, have been investigated. The synthesized CDs were characterized by several physical and optical analyses. The performance of the CDs in terms of bacteria cell imaging and copper (II) ions sensing and removal were also explored. All the CDs possessed a size of 6-7 nm in diameter and the presence of hydroxyl and alkene functional groups indicated the successful transformation of PKS into CDs with carbon core consisting of C = C elementary unit. The highest quantum yield (44.0%) obtained was from the CDs synthesised with DEG as the reacting medium at irradiation period of 1 min. It was postulated that the high boiling point of DEG resulted in a complete carbonisation of PKS into CDs. Subsequently, the absorbance intensity and photoluminescence intensity were also much higher compared to other precursor formulation. All the CDs fluoresced in the bacteria culture, and fluorescence quenching occurred in the presence of heavy metal ions. These showed the potential of CDs synthesised from PKS could be used for cellular imaging and detection as well as removal of heavy metal ions.
Although anionic polyelectrolyte hydrogel beads offer attractive adsorption of cationic dyes, phosphate adsorption is limited by electrostatic interactions. In this work, carboxymethyl cellulose (CMC)/sodium alginate (SA) hydrogel beads were modified with calcium carbonate (CaCO3) and/or bentonite (Be). The compatibility between CaCO3 and Be was proven by the homogeneous surface, as shown in the scanning electron microscopic images. Fourier-transform infrared and X-ray diffraction spectra further confirmed the existence of inorganic filler in the hydrogel beads. Although CMC/SA/Be/CaCO3 hydrogel beads attained the highest methylene blue and phosphate adsorption capacities (142.15 MB mg/g, 90.31 P mg/g), phosphate adsorption was significantly improved once CaCO3 nanoparticles were incorporated into CMC/SA/CaCO3 hydrogel beads. The kinetics of MB adsorption by CMC/SA hydrogel beads with or without inorganic fillers could be described by the pseudo-second-order model under chemical interactions. The phosphate adsorption by CMC/SA/Be/CaCO3 hydrogel beads could be explained by the Elovich model due to heterogeneous properties. The incorporation of Be and CaCO3 also improved the phosphate adsorption through chemical interaction since Langmuir isotherm fitted the phosphate adsorption by CMC/SA/Be/CaCO3 hydrogel beads. Unlike MB adsorption, the reusability of these hydrogel beads in phosphate adsorption reduced slightly after 5 cycles.
The biodegradable, nontoxic, and renewable carboxymethyl cellulose (CMC) hydrogel has been developed into a green adsorbent. However, the weak chemical interaction limits its adsorption capability and reusability. This work incorporated lignin with complex structure and ZnO nanoparticles with photocatalytic properties into CMC hydrogel beads to improve the removal of methylene blue (MB) through chemical interaction. Scanning electron microscopic images and Fourier-transform infrared spectra confirmed the compatibility between lignin and ZnO nanoparticles as well as the increment of active sites for dye removal. The MB adsorption on CMC hydrogel beads was more significantly affected by the temperate and initial concentration compared to contact time, pH, and adsorbent dosage. The MB adsorption capacity of CMC hydrogel was improved to 276.79 mg/g after incorporating lignin and ZnO nanoparticles. The adsorption followed the pseudo-second-order kinetic model and Langmuir isotherm model, indicating chemical adsorption. After 6 cycles, the adsorption capacity was reduced by about 15 %. The UV irradiation could recover and improve MB adsorption capacity of CMC hydrogel beads containing ZnO nanoparticles due to the introduction of reactive oxygen species.
Fat, oil and grease in wastewater generated from household kitchens, restaurants and food processing plants affect sewer systems, water resources and environment adversely. Hence, membrane distillation of saline and oily water was studied using a nearly superhydrophobic membrane developed in this work. Polyvinylidene fluoride (PVDF) membrane incorporated SiO2 nanoparticles was synthesized via phase inversion with dual baths and modified using hexadecyltrimethoxy silane. The volume ratio of silane to ethanol was varied between 1:200 to 1:25. The membrane characteristics were examined using a goniometer, a porometer, scanning electron microscopy (SEM) and Fourier transform infrared spectroscopy (FTIR). The PVDF-SiO2 membrane modified using the volume ratio of 1:50 achieved the highest water contact angle of 141.6° and LEP of 2.642 bar. This membrane was further tested in membrane distillation to observe the permeate flux of distilled water, saline solution (1 M NaCl) as well as saline and oily solution (1 M NaCl; 1,000 ppm of palm oil). The modified PVDF/SiO2 showed high permeate flux which is nearly four times of the permeate flux of neat PVDF membrane, but still susceptible of salt and oil fouling as shown in SEM images.
Carbon capture can be implemented at a large scale only if the CO2 selective materials are abundantly available at low cost. Since the sustainable requirement also elevated, the low-cost and biodegradable cellulosic materials are developed into CO2 selective adsorbent and membranes recently. The applications of cellulose, cellulosic derivatives and nanocellulose as CO2 selective adsorbents and membranes are reviewed here. The fabrication and modification strategies are discussed besides comparing their CO2 separation performance. Cellulose nanofibrils (CNFs) and cellulose nanocrystals (CNCs) isolated from cellulose possess a big surface area for mechanical enhancement and a great number of hydroxyl groups for modification. Nanocellulose aerogels with the large surface area were chemically modified to improve their selectivity towards CO2. Even with the reduction of surface area, amino-functionalized nanocellulose aerogels exhibited the satisfactory chemisorption of CO2 with a capacity of more than 2 mmol/g was recorded. Inorganic fillers such as silica, zeolite and MOFs were further incorporated into nanocellulose aerogels to enhance the physisorption of CO2 by increasing the surface area. Although CO2 adsorbents developed from cellulose and cellulose derivatives were less reported, their applications as the building blocks of CO2 separation membranes had been long studied. Cellulose acetate membranes were commercialized for CO2 separation, but their separation performance could be further improved with silane or inorganic filler. CNCs and CNFs enhanced the CO2 selectivity and permeance through polyvinyl alcohol coating on membranes, but only CNF membranes incorporated with MOFs were explored so far. Although some of these membranes surpassed the upper-bound of Robeson plot, their stability should be further investigated.
Although ultrafiltration (UF) membranes are applicable in wastewater and water treatment, most UF membranes are hydrophobic and susceptible to severe fouling by natural organic matter. In this work, polysulfone (PSf) membrane was blended with silicaluminophosphate (SAPO) nanoparticles, SAPO-34, to study the effect of SAPO-34 incorporation in humic acid (HA) fouling mitigation. The casting solution was prepared by blending 5-20 wt% of SAPO-34 nanoparticles into the mixture of PSf, 1-methyl-2-pyrrolidinone and polyvinyl alcohol at 75 °C. All membrane samples were then prepared using the phase inversion method. Blending SAPO-34 zeolite into PSf membranes caused augmentation in surface hydrophilicity and pore size, leading to higher water permeation. In the HA filtration test, mixed matrix membranes (MMMs) with SAPO-34 zeolite showed reduced HA fouling initiated from pore blocking. The MMM with 20 wt% SAPO-34 loading exhibited the highest increment of water permeation (83%) and maintained about 75% of permeate flux after 2.5 h. However, the SAPO-34 fillers agglomerated in the PSf matrix and induced macrovoid formation on the membrane surface when excessive zeolite was added.
A high concentration of phosphorus in wastewater may lead to excessive algae growth and deoxygenation of the water. In this work, nanofiltration (NF) of phosphorus-rich solutions is studied in order to investigate its potential in removing and recycling phosphorus. Wastewater samples from a pulp and paper plant were first analyzed. Commercial membranes (DK5, MPF34, NF90, NF270, NF200) were characterized and tested in permeability and phosphorus removal experiments. NF90 membranes offer the highest rejection of phosphorus; a rejection of more than 70% phosphorus was achieved for a feed containing 2.5 g/L of phosphorus at a pH <2. Additionally, NF90, NF200 and NF270 membranes show higher permeability than DK5 and MPF34 membranes. The separation performance of NF90 is slightly affected by phosphorus concentration and pressure, which may be due to concentration polarization and fouling. By adjusting the pH to 2 or adding sulfuric acid, the separation performance of NF90 was improved in removing phosphorus. However, the presence of acetic acid significantly impairs the rejection of phosphorus.
Aquaculture activities in developing countries have raised deep concern about nutrient pollution, especially excess phosphorus in wastewater, which leads to eutrophication. NF, NF90, NF450 and XLE membranes were studied to forecast the potential of nanofiltration and low pressure reverse osmosis in the removal of phosphorus from aquaculture wastewater. Cross-sectional morphology, water contact angle, water permeability and zeta potential of these membranes were first examined. Membrane with higher porosity and greater hydrophilicity showed better permeability. Membrane samples also commonly exhibited high zeta potential value in the polyphosphate-rich solution. All the selected membranes removed more than 90% of polyphosphate from the concentrated feed (75 mg/L) at 12 bar. The separation performance of XLE membrane was well maintained at 94.6% even at low pressure. At low feed concentration, more than 70.0% of phosphorus rejection was achieved using XLE membrane. The formation of intermolecular bonds between polyphosphate and the acquired membranes probably had improved the removal of polyphosphate at high feed concentration. XLE membrane was further tested and its rejection of polyphosphate reduced with the decline of pH and the addition of ammonium nitrate.
Membrane distillation (MD) is an attractive technology for the separation of highly saline water used with a polytetrafluoroethylene (PTFE) hollow fiber (HF) membrane. A hydrophobic coating of low-density polyethylene (LDPE) coats the outer surface of the PTFE membrane to resolve membrane wetting as well as increase membrane permeability flux and salt rejection, a critical problem regarding the MD process. LDPE concentrations in coating solution have been studied and optimized. Consequently, the LDPE layer altered membrane morphology by forming a fine nanostructure on the membrane surface that created a hydrophobic layer, a high roughness of membrane, and a uniform LDPE network. The membrane coated with different concentrations of LDPE exhibited high water contact angles of 135.14 ± 0.24 and 138.08 ± 0.01° for membranes M-3 and M-4, respectively, compared to the pristine membrane. In addition, the liquid entry pressure values of LDPE-incorporated PTFE HF membranes (M-1 to M-5) were higher than that of the uncoated membrane (M-0) with a small decrease in the percentage of porosity. The M-3 and M-4 membranes demonstrated higher flux values of 4.12 and 3.3 L m-2 h-1 at 70 °C, respectively. On the other hand, the water permeation flux of 1.95 L m-2 h-1 for M-5 further decreased when LDPE concentration is increased.
Membrane distillation (MD) is a thermal technology for the desalination process that requires a hydrophobic microporous membrane to ensure that the membrane can maintain the liquid-vapor interface. This work aims to enhance the water permeation flux of the previously coated membrane by modifying the surface of the polytetrafluoroethylene hollow fiber (PTFE HF) membrane with a selected non-solvent such as acetone, cyclohexanone, and ethanol in low-density polyethylene as a polymeric coating solution. However, the modification using acetone and cyclohexanone solvents was unsuccessful because a reduction in membrane hydrophobicity was observed. The modified PTFE HF membrane with ethanol content exhibits high wetting resistance with a high water contact angle, which can withstand pore wetting during the direct contact MD process. Since MD operates under a lower operating temperature range (50-90 °C) compared to the conventional distillation, we herein demonstrated that higher flux could be obtained at 7.26 L m-2 h-1. Thus, the process is economically feasible because of lower energy consumption. Performance evaluation of the modified PTFE HF membrane showed a high rejection of 99.69% for sodium chloride (NaCl), indicating that the coated membrane preferentially allowed only water vapor to pass through.
Decorating nanomaterials on graphene oxide (GO) can enhance its adsorption capacity and removal efficiency of water pollutants. In this study, for the first time, nano-sized polylactic acid (PLA) has been successfully decorated on the surface of GO through a facile synthesis approach. The adsorptive efficiency of GO-PLA for removing methylene blue (MB) and tetracycline (TC) from an aqueous solution was examined. The characterization confirmed the successful decoration of PLA on GO nanosheets with the nano size of PLA. It was hypothesized that the PLA was decorated on the surface of GO through covalent bonding between oxygen-containing functional groups and lactide molecules. The optimum adsorption parameters determined were at the adsorbent dose of 0.5 g L-1, pH 4, contact time of 120 min, and temperature of 318 K. The pseudo-second-order kinetic model described the contaminants' adsorption behaviour, and the intraparticle diffusion model revealed that both surface adsorption and intraparticle diffusion controlled the adsorption process. Langmuir isotherm model best described the adsorption behaviour of the pollutants on GO-PLA and demonstrated the maximum monolayer uptake capacities of MB (332.5 mg g-1) and TC (223.7 mg g-1). The adsorption results indicated that the uptake capacities of GO-PLA in comparison to GO have increased by approximately 70% and 110% for MB and TC, respectively. These observations reflect the remarkable role of nano-sized PLA that enhanced the adsorption capacity due to its additional functional group and larger surface area.
Microalgae cultivation using open cultivation systems requires large area and it is susceptible to contamination as well as weather changes. Meanwhile, the closed systems require large capital investment, and they are susceptible to the build-up of dissolved oxygen. Air-liquid interface culture systems with low water-footprint, but high packing density can be used for microalgae cultivation if low-cost culture scaffolds are available. In this study, cellulose-based scaffolds were synthesized using NaOH/urea aqueous solution as the solvent. Titanium dioxide (TiO2), silica gel and polyethylene glycol 1000 (PEG 1000) nanoparticles were added into the membrane scaffolds to increase the hydrophilicity of nutrient absorbing to support the growth of microalgae. The membrane scaffolds were characterized by FTIR, SEM, contact angle, porosity and porometry. All three nanoparticles additives showed their ability in reducing the contact angle of membrane scaffolds from 63.4 ± 2.3° to a range of 52.6 ± 1.2° to 38.8 ± 1.5° due to the hydrophilic properties of the nanoparticles. The decreasing in pore size when nanoparticles were added did not affect the porosity of membrane scaffolds. Cellulose membrane scaffold with TiO2 showed the highest percentage of microalgae Navicula incerta growth rate of 22.1% because of the antibacterial properties of TiO2 in lowering the risk of cell contamination and enhancing the growth of N. incerta. The results exhibited that cellulose-based scaffold with TiO2 added could be an effective support in plant cell culture field.
Culture scaffolds allow microalgae cultivation with minimum water requirement using the air-liquid interface approach. However, the stability of cellulose-based scaffolds in microalgae cultivation remains questionable. In this study, the stability of regenerated cellulose culture scaffolds was enhanced by adjusting TiO2 loading and casting gap. The membrane scaffolds were synthesized using cellulose dissolved in NaOH/urea aqueous solution with various loading of TiO2 nanoparticles. The TiO2 nanoparticles were embedded into the porous membrane scaffolds as proven by Fourier transform infrared spectra, scanning electron microscopic images, and energy-dispersive X-ray spectra. Although surface hydrophilicity and porosity were enhanced by increasing TiO2 and casting gap, the scaffold pore size was reduced. Cellulose membrane scaffold with 0.05 wt% of TiO2 concentration and thickness of 100 μm attained the highest percentage of Navicula incerta growth rate, up to 37.4%. The membrane scaffolds remained stable in terms of weight, porosity and pore size even they were immersed in acidic solution, hydrogen peroxide or autoclaved at 121 °C for 15 min. The optimal cellulose membrane scaffold is with TiO2 loading of 0.5 wt% and thickness of 100 μm, resulting in supporting the highest N. incerta growth rate and and exhibits good membrane stability.
Traditionally existing 2D culture scaffold has been inappropriately validated due to the failure in generating the precise therapeutic response. Therefore, this leads to the fabrication of 3D culture scaffold resolving the limitations in the in vivo environment. In recent years, tissue engineering played an important role in the field of bio-medical engineering. Biopolymer material, a novel natural material with excellent properties of nontoxic and biodegradable merits can be served as culture scaffold. This review summarizes the modifications of natural biopolymeric culture scaffold with different crosslinkers and their application. In addition, this review provides the recent progress of natural biopolymeric culture scaffold mainly focusing on their properties, synthesizing and modification and application.