The recognition of cellulose nanofibrils (CNF) in the past years as a high prospect material has been prominent, but the impractical cellulose extraction method from biomass remained as a technological barrier for industrial practice. In this study, the telescopic approach on the fractionation of lignin and cellulose was performed by organosolv extraction and catalytic oxidation from oil palm empty fruit bunch fibers. The integration of these techniques managed to synthesize CNF in a short time. Aside from the size, the zeta potential of CNF was measured at -41.9 mV, which allow higher stability of the cellulose in water suspension. The stability of CNF facilitated a better dispersion of Fe(0) nanoparticles with the average diameter size of 52.3-73.24 nm through the formulation of CNF/Fe(0). The total uptake capacity of CNF towards 5-fluorouracil was calculated at 0.123 mg/g. While the synergistic reactions of adsorption-oxidation were significantly improved the removal efficacy three to four times greater even at a high concentration of 5-fluorouracil. Alternatively, the sludge generation after the oxidation reaction was completely managed by the encapsulation of Fe(0) nanoparticles in regenerated cellulose.
Three-Dimentional (3-D) printing is currently a popular printing technique that is used in many sectors. Potentially, this technology is expected to replace conventional manufacturing in the coming years. It is accelerating in gaining attention due to its design freedom where objects can be produced without imagination boundaries. The review presents a perspective on the application of 3-D printing application based on various fields. However, the ordinary 3-D printed products with a single type of raw often lack robustness leading to broken parts. Improving the mechanical property of a 3-D printed part is crucial for its applications in many fields. One of the promising solutions is to incorporate nanoparticles or fillers into the raw material. The review aims to provide information about the types of additive manufacturing. There are few types of raw materials can be used as foundation template in the printing, enhanced properties of the printed polymer nanocomposites with different types of nanoparticles as additives in the printing. The article reviews the advantages and disadvantages of different materials that are used as raw materials or base materials in 3-D printing. This can be a guideline for the readers to compare and analyse the raw materials prior to a decision on the type of material to be selected. The review prepares an overview for the researchers to choose the types of nanoparticles to be added in the printing of the products depending on the targeted application. With the added functionality of the 3-D polymer nanocomposites, it will help in widespread of the application of 3-D printing technology in various sector.
Development of polyurethane foam (PUF) containing bio-based components is a complex process that requires extensive studies. This work reports on the production of rigid PUFs from polyol obtained via liquefaction of oil palm empty fruit bunch (EFB) biomass with different isocyanate (NCO) indexes. The effect of the NCO index on the physical, chemical and compressive properties of the liquefied EFB-based PUF (EFBPUF) was evaluated. The EFBPUFs showed a unique set of properties at each NCO index. Foaming properties had affected the apparent density and cellular morphology of the EFBPUFs. Increasing NCO index had increased the crosslink density and dimensional stability of the EFBPUFs via formation of isocyanurates, which had also increased their thermal stability. Combination of both foaming properties and crosslink density of the EFBPUFs had influenced their respective compressive properties. The EFBPUF produced at the NCO index of 120 showed the optimum compressive strength and released the least toxic hydrogen cyanide (HCN) gas under thermal degradation. The normalized compressive strength of the EFBPUF at the NCO index of 120 is also comparable with the strength of the PUF produced using petrochemical polyol.
A series of polystyrene nanoparticles (PS-1, PS-2, PS-3, and PS-4) in aqueous solutions were investigated in terms of morphological structure, size, and size distribution. Synchrotron small-angle X-ray scattering analysis (SAXS) was carried out, providing morphology details, size and size distribution on the particles. PS-1, PS-2, and PS-3 were confirmed to behave two-phase (core and shell) spherical shapes, whereas PS-4 exhibited a single-phase spherical shape. They all revealed very narrow unimodal size distributions. The structural parameter details including radial density profile were determined. In addition, the presence of surfactant molecules and their assemblies were detected for all particle solutions, which could originate from their surfactant-assisted emulsion polymerizations. In addition, dynamic light scattering (DLS) analysis was performed, finding only meaningful hydrodynamic size and intensity-weighted mean size information on the individual PS solutions because of the particles' spherical nature. In contrast, the size distributions were extracted unrealistically too broad, and the volume- and number-weighted mean sizes were too small, therefore inappropriate to describe the particle systems. Furthermore, the DLS analysis could not detect completely the surfactant and their assemblies present in the particle solutions. Overall, the quantitative SAXS analysis confirmed that the individual PS particle systems were successfully prepared with spherical shape in a very narrow unimodal size distribution.
Wastewater generated from industries seriously impacts the environment. Conventional biological and physiochemical treatment methods for wastewater containing organic molecules have some limitations. Therefore, identifying other alternative methods or processes that are more suitable to degrade organic molecules and lower chemical oxygen demand (COD) in wastewater is necessary. Heterogeneous Fenton processes and persulfate (PS) oxidation are advanced oxidation processes (AOPs) that degrade organic pollutants via reactive radical species. Therefore, in this study, limonite powder was incorporated into porous regenerated chitosan fibers and further used as a heterogeneous catalyst to decompose methylene blue (MB) via sulfate radical-based AOPs. Limonite was used as a heterogeneous catalyst in this process to generate the persulfate radicals (SO4-·) that initiate the decolorization process. Limonite-chitosan fibers were produced to effectively recover the limonite powder so that the catalyst can be reused repeatedly. The formation of limonite-chitosan fibers viewed under a field emission scanning electron microscope (FESEM) showed that the limonite powder was well distributed in both the surface and cross-section area. The effectiveness of limonite-chitosan fibers as a catalyst under PS activation achieved an MB decolorization of 78% after 14 min. The stability and reusability of chitosan-limonite fibers were evaluated and measured in cycles 1 to 10 under optimal conditions. After 10 cycles of repeated use, the limonite-chitosan fiber maintained its performance up to 86%, revealing that limonite-containing chitosan fibers are a promising reusable catalyst material.
Wearable energy storage devices require high mechanical stability and high-capacitance flexible electrodes. In this study, we design a flexible supercapacitor electrode consisting of 1-dimensional carbon nanotubes (CNT), cellulose nanofibrils (CNF), and manganese dioxide nanowires (MnO2 NWs). The flexible and conductive CNT/CNF-MnO2 NWs suspension was first prepared via ultrasonic dispersion approach, followed by vacuum filtration and hot press to form the composite paper electrode. The morphological studies show entanglement between CNT and CNF, which supports the mechanical properties of the composite. The CNT/CNF-MnO2 NWs electrode exhibits lower resistance when subjected to various bending angles (-120-+120°) compared to the CNT/CNF electrode. In addition, the solid-state supercapacitor also shows a high energy density of 38 μWh cm-2 and capacitance retention of 83.2% after 5000 cycles.
Plastic waste poses a significant challenge for the environment, particularly smaller plastic products that are often difficult to recycle or collect. In this study, we developed a fully biodegradable composite material from pineapple field waste that is suitable for small-sized plastic products that are difficult to recycle, such as bread clips. We utilized starch from waste pineapple stems, which is high in amylose content, as the matrix, and added glycerol and calcium carbonate as the plasticizer and filler, respectively, to improve the material's moldability and hardness. We varied the amounts of glycerol (20-50% by weight) and calcium carbonate (0-30 wt.%) to produce composite samples with a wide range of mechanical properties. The tensile moduli were in the range of 45-1100 MPa, with tensile strengths of 2-17 MPa and an elongation at break of 10-50%. The resulting materials exhibited good water resistance and had lower water absorption (~30-60%) than other types of starch-based materials. Soil burial tests showed that the material completely disintegrated into particles smaller than 1 mm within 14 days. We also created a bread clip prototype to test the material's ability to hold a filled bag tightly. The obtained results demonstrate the potential of using pineapple stem starch as a sustainable alternative to petroleum-based and biobased synthetic materials in small-sized plastic products while promoting a circular bioeconomy.
In order to reduce our dependence on nonrenewable plastics and solve the problem of non-biodegradable plastic waste, there has been much attention paid to the development of biodegradable plastics from natural resources. Starch-based materials have been widely studied and developed for commercial production, primarily from corn and tapioca. However, the use of these starches could generate food security problems. Therefore, the use of alternative starch sources, such as agricultural waste, would be of great interest. In this work, we investigated the properties of films prepared from pineapple stem starch, which has a high amylose content. Pineapple stem starch (PSS) films and glycerol-plasticized PSS films were prepared and characterized using X-ray diffraction and water contact angle measurements. All films exhibited some degree of crystallinity, making them water-resistant. The effect of glycerol content on mechanical properties and gas (oxygen, carbon dioxide and water vapor) transmission rates was also studied. The tensile modulus and tensile strength of the films decreased with increasing glycerol content, while gas transmission rates increased. Preliminary studies showed that coatings made from PSS films could slow down the ripening process of bananas and extend their shelf life.
Star-shaped polymers are very attractive because of their potential application ability in various technological areas due to their unique molecular topology. Thus, information on the molecular structure and chain characteristics of star polymers is essential for gaining insights into their properties and finding better applications. In this study, we report molecular structure details and chain characteristics of 17-armed polystyrenes in various molecular weights: 17-Arm(2k)-PS, 17-Arm(6k)-PS, 17-Arm(10k)-PS, and 17-Arm(20k)-PS. Quantitative X-ray scattering analysis using synchrotron radiation sources was conducted for this series of star polymers in two different solvents (cyclohexane and tetrahydrofuran), providing a comprehensive set of three-dimensional structure parameters, including radial density profiles and chain characteristics. Some of the structural parameters were crosschecked by qualitative scattering analysis and dynamic light scattering. They all were found to have ellipsoidal shapes consisting of a core and a fuzzy shell; such ellipse nature is originated from the dendritic core. In particular, the fraction of the fuzzy shell part enabling to store desired chemicals or agents was confirmed to be exceptionally high in cyclohexane, ranging from 74 to 81%; higher-molecular-weight star polymer gives a larger fraction of the fuzzy shell. The largest fraction (81%) of the fuzzy shell was significantly reduced to 52% in tetrahydrofuran; in contrast, the lowest fraction (19%) of core was increased to 48%. These selective shell contraction and core expansion can be useful as a key mechanism in various applications. Overall, the 17-armed polystyrenes of this study are suitable for applications in various technological fields including smart deliveries of drugs, genes, biomedical imaging agents, and other desired chemicals.
In this work, lipase from Candida rugosa was immobilized onto chitosan/graphene oxide beads. This was to provide an enzyme-immobilizing carrier with excellent enzyme immobilization activity for an enzyme group requiring hydrophilicity on the immobilizing carrier. In addition, this work involved a process for the preparation of an enzymatically active product insoluble in a reaction medium consisting of lauric acid and oleyl alcohol as reactants and hexane as a solvent. This product enabled the stability of the enzyme under the working conditions and allowed the enzyme to be readily isolated from the support. In particular, this meant that an enzymatic reaction could be stopped by the simple mechanical separation of the "insoluble" enzyme from the reaction medium. Chitosan was incorporated with graphene oxide because the latter was able to enhance the physical strength of the chitosan beads by its superior mechanical integrity and low thermal conductivity. The X-ray diffraction pattern showed that the graphene oxide was successfully embedded within the structure of the chitosan. Further, the lipase incorporation on the beads was confirmed by a thermo-gravimetric analysis. The lipase immobilization on the beads involved the functionalization with coupling agents, N-hydroxysulfosuccinimide sodium (NHS) and 1-ethyl-(3-dimethylaminopropyl) carbodiimide (EDC), and it possessed a high enzyme activity of 64 U. The overall esterification conversion of the prepared product was 78% at 60 °C, and it attained conversions of 98% and 88% with commercially available lipozyme and novozyme, respectively, under similar experimental conditions.
Here, a stable derivative of cellulose, called cellulose carbamate (CC), was produced from Kenaf (Hibiscus cannabinus) core pulp (KCP) and urea with the aid of a hydrothermal method. Further investigation was carried out for the amount of nitrogen yielded in CC as different urea concentrations were applied to react with cellulose. The effect of nitrogen concentration of CC on its solubility in a urea-alkaline system was also studied. Regenerated cellulose products (hydrogels and aerogels) were fabricated through the rapid dissolution of CC in a urea-alkaline system. The morphology of the regenerated cellulose products was viewed under Field emission scanning electron microscope (FESEM). The transformation of allomorphs in regenerated cellulose products was examined by X-ray diffraction (XRD). The transparency of regenerated cellulose products was determined by Ultraviolet-visible (UV-Vis) spectrophotometer. The degree of swelling (DS) of regenerated cellulose products was also evaluated. This investigation provides a simple and efficient procedure of CC determination which is useful in producing regenerated CC products.
Silver nanoparticles and silver-graphene oxide nanocomposites were fabricated using a rapid and green microwave irradiation synthesis method. Silver nanoparticles with narrow size distribution were formed under microwave irradiation for both samples. The silver nanoparticles were distributed randomly on the surface of graphene oxide. The Fourier transform infrared and thermogravimetry analysis results showed that the graphene oxide for the AgNP-graphene oxide (AgGO) sample was partially reduced during the in situ synthesis of silver nanoparticles. Both silver nanoparticles and AgGO nanocomposites exhibited stronger antibacterial properties against Gram-negative bacteria (Salmonella typhi and Escherichia coli) than against Gram-positive bacteria (Staphyloccocus aureus and Staphyloccocus epidermidis). The AgGO nanocomposites consisting of approximately 40 wt.% silver can achieve antibacterial performance comparable to that of neat silver nanoparticles.
: Hydrogen (H2) is a clean energy carrier which can help to solve environmental issues with the depletion of fossil fuels. Sodium borohydride (NaBH4) is a promising candidate material for solid state hydrogen storage due to its huge hydrogen storage capacity and nontoxicity. However, the hydrolysis of NaBH4 usually requires expensive noble metal catalysts for a high H2 generation rate (HGR). Here, we synthesized high-aspect ratio copper nanowires (CuNWs) using a hydrothermal method and used them as the catalyst for the hydrolysis of NaBH4 to produce H2. The catalytic H2 generation demonstrated that 0.1 ng of CuNWs could achieve the highest volume of H2 gas in 240 min. The as-prepared CuNWs exhibited remarkable catalytic performance: the HGR of this study (2.7 × 1010 mL min-1 g-1) is ~3.27 × 107 times higher than a previous study on a Cu-based catalyst. Furthermore, a low activation energy (Ea) of 42.48 kJ mol-1 was calculated. Next, the retreated CuNWs showed an outstanding and stable performance for five consecutive cycles. Moreover, consistent catalytic activity was observed when the same CuNWs strip was used for four consecutive weeks. Based on the results obtained, we have shown that CuNWs can be a plausible candidate for the replacement of a costly catalyst for H2 generation.
Adsorption is the most widely used technique for advanced wastewater treatment. The preparation and application of natural renewable and environmentally friendly materials makes this process easier and more profitable. Chitosan is often used as an effective biomaterial in the adsorption world because of its numerous functional applications. Chitosan is one of the most suitable and functionally flexible adsorbents because it contains hydroxyl (-OH) and amine (-NH2) groups. The adsorption capacity and selectivity of chitosan can be further improved by introducing additional functions into its basic structure. Owing to its unique surface properties and adsorption ability of chitosan, the development and application of chitosan nanomaterials has gained significant attention. Here, recent research on chitosan nanoparticles is critically reviewed by comparing various methods for their synthesis with particular emphasis on the role of experimental conditions, limitations, and applications in water and wastewater treatment. The recovery of pollutants using magnetic nanoparticles is an important treatment process that has contributed to additional development and sustainable growth. The application of such nanoparticles in the recovery metals, which demonstrates a "close loop technology" in the current scenarios, is also presented in this review.
Copper nanowires (CuNWs) with a high aspect ratio of ~2600 have been successfully synthesized by using a facile hydrothermal method. The reductions of 4-nitrophenol (4-NP) to 4-aminophenol (4-AP) and methylene blue (MB) to leucomethylene blue (LMB) by using sodium borohydride (NaBH4) were used as models to test the catalytic activity of CuNWs. We showed that by increasing the CuNWs content, the rate of reduction increased as well. The CuNWs showed an excellent catalytic performance where 99% reduction of 4-NP to 4-AP occurred in just 60 s by using only 0.1 pg of CuNWs after treatment with glacial acetic acid (GAA). The rate constant (kapp) and activity factor (K) of this study is 18 and ~1010 fold in comparison to previous study done with no GAA treatment applied, respectively. The CuNWs showed an outstanding catalytic activity for at least ten consecutive reusability tests with a consistent result in 4-NP reduction. In clock reaction of MB, approximately 99% of reduction of MB into LMB was achieved in ~5 s by using 2 μg CuNWs. Moreover, the addition of NaOH can improve the rate and degree of recolorization of LMB to MB.
In this study, biodegradable starch film was developed from pineapple stem waste as a substitute for non-biodegradable petroleum-based films for single-use applications where strength is not too demanding. High amylose starch from a pineapple stem was used as the matrix. Glycerol and citric acid were used as additives to adjust the ductility of the material. Glycerol content was fixed at 25% while that of citric acid varied from 0 to 15% by weight of starch. Films with a wide range of mechanical properties can be prepared. As more citric acid is added, the film becomes softer and weaker, and has greater elongation at the break. Properties range from a strength of about 21.5 MPa and 2.9% elongation to a strength of about 6.8 MPa and 35.7% elongation. An X-ray diffraction study showed that the films were semi-crystalline. The films were also found to be water-resistant and can be heat-sealed. An example of a single-use package was demonstrated. A soil burial test confirmed that the material was biodegradable and completely disintegrated into sizes smaller than 1 mm within one month.
The sorption of Fe(2+) onto unbleached kraft fibre was investigated at different conditions such as pH, temperature, and concentrations. The sorption, which increased with concentration and temperature, followed the Langmuir isotherm. Thermodynamically, the process was spontaneous and endothermic. It was found that the precipitation of Fe(2+) was highly dependent on pH and reached 100% when pH exceeded approximately 8.
A simple single-stage approach, based on the hydrothermal technique, has been introduced to synthesize reduced graphene oxide/titanium dioxide nanocomposites. The titanium dioxide nanoparticles are formed at the same time as the graphene oxide is reduced to graphene. The triethanolamine used in the process has two roles. It acts as a reducing agent for the graphene oxide as well as a capping agent, allowing the formation of titanium dioxide nanoparticles with a narrow size distribution (~20 nm). Transmission electron micrographs show that the nanoparticles are uniformly distributed on the reduced graphene oxide nanosheet. Thermogravimetric analysis shows the nanocomposites have an enhanced thermal stability over the original components. The potential applications for this technology were demonstrated by the use of a reduced graphene oxide/titanium dioxide nanocomposite-modified glassy carbon electrode, which enhanced the electrochemical performance compared to a conventional glassy carbon electrode when interacting with mercury(II) ions in potassium chloride electrolyte.
Graphene has attracted much attention from researchers due to its interesting mechanical, electrochemical, and electronic properties. It has many potential applications such as polymer filler, sensor, energy conversion, and energy storage devices. Graphene-based nanocomposites are under an intense spotlight amongst researchers. A large amount of graphene is required for preparation of such samples. Lately, graphene-based materials have been the target for fundamental life science investigations. Despite graphene being a much sought-after raw material, the drawbacks in the preparation of graphene are that it is a challenge amongst researchers to produce this material in a scalable quantity and that there is a concern about its safety. Thus, a simple and efficient method for the preparation of graphene oxide (GO) is greatly desired to address these problems. In this work, one-pot chemical oxidation of graphite was carried out at room temperature for the preparation of large-area GO with ~100% conversion. This high-conversion preparation of large-area GO was achieved using a simplified Hummer's method from large graphite flakes (an average flake size of 500 μm). It was found that a high degree of oxidation of graphite could be realized by stirring graphite in a mixture of acids and potassium permanganate, resulting in GO with large lateral dimension and area, which could reach up to 120 μm and ~8000 μm(2), respectively. The simplified Hummer's method provides a facile approach for the preparation of large-area GO.
Three-dimensional assembly of graphene hydrogel is rapidly attracting the interest of researchers because of its wide range of applications in energy storage, electronics, electrochemistry, and waste water treatment. Information on the use of graphene hydrogel for biological purposes is lacking, so we conducted a preliminary study to determine the suitability of graphene hydrogel as a substrate for cell growth, which could potentially be used as building blocks for biomolecules and tissue engineering applications.