Surface Modified Activated Carbons: Sustainable Bio-Based Materials for Environmental Remediation.

Global warming and water/air contamination caused by human activities are major challenges in environmental pollution and climate change. The improper discharge of a large amount of agro-forest byproduct is accelerating these issues mainly in developing countries. The burning of agricultural byproducts causes global warming, whereas their improper waste management causes water/air pollution. The conversion of these waste materials into effective smart materials can be considered as a promising strategy in waste management and environmental remediation. Over the past decades, activated carbons (ACs) have been prepared from various agricultural wastes and extensively used as adsorbents. The adsorption capacity of ACs is linked to a well-developed porous structure, large specific surface area, and rich surface functional moieties. Activated carbon needs to increase their adsorption capacity, especially for specific adsorbates, making them suitable for specific applications, and this is possible by surface modifications of their surface chemistry. The modifications of surface chemistry involve the introduction of surface functional groups which can be carried out by various methods such as acid treatment, alkaline treatment, impregnation, ozone treatment, plasma treatment, and so on. Depending on the treatment methods, surface modification mainly affects surface chemistry. In this review, we summarized several modification methods for agricultural-waste-based ACs. In addition, the applications of AC for the adsorption of various pollutants are highlighted.

Decoration of Zinc Oxide Nanorods into the Surface of Activated Carbon Obtained from Agricultural Waste for Effective Removal of Methylene Blue Dye.

Zinc oxide (ZnO) nanorods incorporated activated carbon (AC) composite photocatalyst was synthesized using a hydrothermal process. The AC was prepared from lapsi (Choerospondias axillaris) seed stone, an agricultural waste product, found in Nepal by the chemical activation method. An aqueous suspension of AC with ZnO precursor was subjected to the hydrothermal treatment at 140 °C for 2 h to decorate ZnO rods into the surface of AC. As-obtained ZnO nanorods decorated activated carbon (ZnO/AC) photocatalyst was characterized by various techniques, such as scanning electron microscopy (SEM), X-ray diffraction (XRD), and photoluminescence (PL) spectroscopy. Results showed that highly crystalline hexagonal ZnO nanorods were effectively grown on the surface of porous AC. The photocatalytic property of the as-prepared ZnO/AC composite was studied by degrading methylene blue (MB) dye under UV-light irradiation. The ZnO/AC composite showed better photocatalytic property than that of the pristine ZnO nanorods. The enhanced photocatalytic performance in the case of the ZnO/AC composite is attributed to the combined effects of ZnO nanorods and AC.

Fe1-xS Modified TiO2 NPs Embedded Carbon Nanofiber Composite via Electrospinning: A Potential Electrode Material for Supercapacitors.

Fe1-xS-TiO2 nanoparticles embedded carbon nanofibers (Fe1-xS-TiO2/CNFs) composite as a supercapacitor electrode material has been reported in the present work. The Fe1-xS-TiO2/CNFs composite was fabricated by electrospinning technique followed by carbonization under argon atmosphere and characterized by the state-of-art techniques. The electrochemical studies were carried out in a 2 M KOH electrolyte solution. The synthesized material showed a specific capacitance value of 138 F/g at the current density of 1 A/g. Further, the capacitance retention was about 83%. The obtained results indicate that the Fe1-xS-TiO2/CNFs composite can be recognized as electrode material in supercapacitor.

Three-dimensional cellulose sponge: Fabrication, characterization, biomimetic mineralization, and in vitro cell infiltration.

In this study, cellulose based scaffolds were produced by electrospinning of cellulose acetate (CA) solution followed by its saponification with NaOH/ethanol system for 24h. The resulting nonwoven cellulose mat was treated with sodium borohydride (SB) solution. In situ hydrolysis of SB solution into the pores of the membrane produced hydrogen gas resulting a three-dimensional (3D) cellulose sponge. SEM images demonstrated an open porous and loosely packed fibrous mesh compared to the tightly packed single-layered structure of the conventional electrospun membrane. 3D cellulose sponge showed admirable ability to nucleate bioactive calcium phosphate (Ca-P) crystals in simulated body fluid (SBF) solution. SEM-EDX and X-ray diffraction studies revealed that the minerals deposited on the nanofibers have the nonstoichiometric composition similar to that of hydroxyapatite, the mineralized component of the bone. 3D cellulose sponge exhibited the better cell infiltration, spreading and proliferation compared to 2D cellulose mat. Therefore, a facile fabrication of 3D cellulose sponge with improved mineralization represents an innovative strategy for the bone tissue engineering applications.

In Situ Generation of Cellulose Nanocrystals in Polycaprolactone Nanofibers: Effects on Crystallinity, Mechanical Strength, Biocompatibility, and Biomimetic Mineralization.

Post-electrospinning treatment is a facile process to improve the properties of electrospun nanofibers for various applications. This technique is commonly used when direct electrospinning is not a suitable option to fabricate a nonwoven membrane of the desired polymer in a preferred morphology. In this study, a representative natural-synthetic hybrid of cellulose acetate (CA) and polycaprolactone (PCL) in different ratios was fabricated using an electrospinning process, and CA in the hybrid fiber was transformed into cellulose (CL) by post-electrospinning treatment via alkaline saponification. Scanning electron microscopy was employed to study the effects of polymer composition and subsequent saponification on the morphology of the nanofibers. Increasing the PCL content in the PCL/CA blend solution caused a gradual decrease in viscosity, resulting in smoother and more uniform fibers. The saponification of fibers lead to pronounced changes in the physicochemical properties. The crystallinity of the PCL in the composite fiber was varied according to the composition of the component polymers. The water contact angle was considerably decreased (from 124° to less than 20°), and the mechanical properties were greatly enhanced (Young's Modulus was improved by ≈20-30 fold, tensile strength by 3-4 fold, and tensile stress by ≈2-4 fold) compared to those of PCL and PCL/CA membranes. Regeneration of cellulose chains in the nanofibers increased the number of hydroxyl groups, which increased the hydrogen bonding, thereby improving the mechanical properties and wettability of the composite nanofibers. The improved wettability and presence of surface functional groups enhanced the ability to nucleate bioactive calcium phosphate crystals throughout the matrix when exposed to a simulated body fluid solution. Experimental results of cell viability assay, confocal microscopy, and scanning electron microscopy imaging showed that the fabricated nanofibrous membranes have excellent ability for MC3T3-E1 cell proliferation and growth. Given the versatility and widespread use of cellulose-synthetic hybrid systems in the construction of tissue-engineered scaffolds, this work provides a novel strategy to fabricate the biopolymer-based materials for applications in tissue engineering and regenerative medicine.

Immobilization of TiO2 nanofibers on reduced graphene sheets: Novel strategy in electrospinning.

A simple and efficient approach is developed to immobilize TiO2 nanofibers onto reduced graphene oxide (RGO) sheets. Here, TiO2 nanofiber-intercalated RGO sheets are readily produced by two-step procedure involving the use of electrospinning process to fabricate TiO2 precursor containing polymeric fibers on the surface of GO sheets, followed by simultaneous TiO2 nanofibers formation and GO reduction by calcinations. GO sheets deposited on the collector during electrospinning/electrospray can act as substrate on to which TiO2 precursor containing polymer nanofibers can be deposited which give TiO2 NFs doped RGO sheets on calcinations. Formation of corrugated structure cavities of graphene sheets decorated with TiO2 nanofibers on their surface demonstrates that our method constitutes an alternative top-down strategy toward fabricating verities of nanofiber-decorated graphene sheets. It was found that the synthesized TiO2/RGO composite revealed a remarkable increased in photocatalytic activity compared to pristine TiO2 nanofibers. Therefore, engineering of TiO2 nanofiber-intercalated RGO sheets using proposed facile technique can be considered a promising method for catalytic and other applications.

In-situ deposition of silver-iron oxide nanoparticles on the surface of fly ash for water purification.

In this study, a fly ash based composite, Ag-iron oxide/fly ash, was synthesized via a facile one-pot hydrothermal process using fly ash, ferrous chloride, and silver nitrate as precursors. Field emission scanning electron microscopy (FE-SEM), EDX, transmission electron microscopy (TEM), X-ray diffraction (XRD), Fourier transform infra-red spectroscopy (FTIR), Photoluminescence (PL) and Brunauer-Emmett-Teller (BET) surface area measurement confirmed the formation of composite particle. FA provided a suitable surface for the in-situ deposition of Fe3O4 and Ag NPs during hydrothermal treatment. As a result, the particle size of Fe3O4 and Ag NPs was sufficiently decreased, and the surface area of the NPs as well as, a whole matrix was increased. The antimicrobial activity of the composite was accessed by Escherichia coli inhibition assay. Lead(II) ion adsorption efficiency of the composite was analyzed from a series of batch adsorption experiments (the effects of concentration, contact time, pH and adsorbent dose on the adsorption of Pb(II) ion from aqueous solution). Results indicated that as-synthesized composite has high antibacterial capacity, and the metal ions uptake efficiency compared to fly ash particle. Furthermore, incorporation Fe3O4 NPs onto the fly ash make it easily separable from a reaction system using an external magnet. The composite synthesis protocol is a simple method that utilizes a readily available industrial byproduct to produce a unique composite for environmental remediation.

Effect of laser polishing on the surface roughness and corrosion resistance of Nitinol stents.

In this paper, we investigated the effect of laser polishing at different treatment times on the surface roughness and corrosion resistance of a biliary nickel-titanium (NiTi or Nitinol) stent. A specific area of the stent wire surface was checked for changes in roughness by scanning electron microscopy (SEM) and a noncontact profilometer. The corrosion resistance was assessed by potentiodynamic polarization test and electrochemical impedance spectroscopy. The surface characterization revealed that laser polishing reduced the surface roughness of stent by 34-64% compared to that of the as-received stent surface condition depending on the treatment time (i.e., 700-1600 µm). Measurements using potentiodynamic polarization in simulated body fluid solution showed better anti-corrosion performance of laser-polished stent compared to magnetically-polished stent and has comparable corrosion resistance with the as-received stent condition. In this paper, we have shown a preliminary study on the potential of laser polishing for the improvement of surface roughness of stent without affecting much its corrosion resistance.

Electrospun propolis/polyurethane composite nanofibers for biomedical applications.

Tissue engineering requires functional polymeric membrane for adequate space for cell migration and attachment within the nanostructure. Therefore, biocompatible propolis loaded polyurethane (propolis/PU) nanofibers were successfully prepared using electrospinning of propolis/PU blend solution. Here, composite nanofibers were subjected to detailed analysis using electron microscopy, FT-IR spectroscopy, thermal gravimetric analysis (TGA), and mechanical properties and water contact angle measurement. FE-SEM images revealed that the composite nanofibers became point-bonded with increasing amounts of propolis in the blend due to its adhesive properties. Incorporation of small amount of propolis through PU matrix could improve the hydrophilicity and mechanical strength of the fibrous membrane. In order to assay the cytocompatibility and cell behavior on the composite scaffolds, fibroblast cells were seeded on the matrix. Results suggest that the incorporation of propolis into PU fibers could increase its cell compatibility. Moreover, composite nanofibers have effective antibacterial activity. Therefore, as-synthesized nanocomposite fibrous mat has great potentiality in wound dressing and skin tissue engineering.

Synthesis and photocatalytic activities of CdS/TiO2 nanoparticles supported on carbon nanofibers for high efficient adsorption and simultaneous decomposition of organic dyes.

CdS/TiO2 NPs-decorated carbon nanofibers were prepared by a simple electrospinning method followed by the calcination under argon atmosphere. As-synthesized nanocomposites exhibited a strong photocatalytic activity for decomposition of methylene blue (MB), reactive black 5, and reactive orange 16 under visible light radiation for many successive cycles. Moreover, in the dark, the carbon content revealed very good adsorption behavior as 95% of the dye was removed within 5 min, however less adsorption capacity was observed upon successive cycles. Therefore, the enhanced photocatalytic performance for the introduced nanofibers might be attributed to the adsorption characteristic of carbon nanofiber and the known photocatalytic activities of the TiO2 and CdS photocatalysts.

One-step fabrication of multifunctional composite polyurethane spider-web-like nanofibrous membrane for water purification.

A stable silver-doped fly ash/polyurathene (Ag-FA/PU) nanocomposite multifunctional membrane is prepared by a facile one-step electrospinning process using fly ash particles (FAPs). Colloidal solution of PU with FAPs and Ag metal precursor was subjected to fabricate nanocomposite spider-web-like membrane using electrospinning process. Presence of N,N-dimethylformamide (solvent of PU) led to reduce silver nitrate into Ag NPs. Incorporation of Ag NPs and FAPs through electrospun PU fibers is proven through electron microscopy and spectroscopic techniques. Presence of these NPs on PU nanofibers introduces several potential physicochemical properties such as spider-web-like nano-neeting for NPs separation, enhanced absorption capacity to remove carcinogenic arsenic (As) and toxic organic dyes, and antibacterial properties with reduce bio-fouling for membrane filter application. Preliminary observations used for above-mentioned applications for water treatment showed that it will be an economically and environmentally friendly nonwoven matrix for water purification. This simple approach highlights new avenues about the utilization of one pollutant material to control other pollutants in scalable and inexpensive ways.

Synthesis, characterization, and mineralization of polyamide-6/calcium lactate composite nanofibers for bone tissue engineering.

Polyamide-6 nanofibers containing calcium lactate (CL) on their surface were prepared by neutralization of lactic acid (LA) in core-shell structured polyamide-6/LA electrospun fibers. First, simple blending of LA with polyamide-6 solution was used for electrospinning which interestingly formed a thin LA layer around polyamide-6 nanofibers (core-shell structure) and then subsequent conversion of this LA into calcium lactate via neutralization using calcium base. FE-SEM and TEM images revealed that plasticizer capacity of LA led the formation of point-bonded structure due to the formation of shell layer of LA and core of polyamide-6. The bone formation ability of polyamide-6/calcium lactate composite fibers was evaluated by incubating in biomimetic simulated body fluid (SBF). The SBF incubation test confirmed the faster deposition of large amount of calcium phosphate around the composite polyamide-6/calcium lactate fibers compared to pristine polyamide-6. This study demonstrated a simple post electrospinning calcium compound coating technique of polymeric nanofibers for enhancing the bone biocompatibility of polyamide-6 fibers.

Effect of polymer molecular weight on the fiber morphology of electrospun mats.

In this work, different fractions of solvent-induced polymer degraded solution were mixed with freshly prepared solution of same polymer, and its effect on fiber morphology of electrospun mats was investigated. Nylon-6 solution in formic acid was allowed to degrade for 3 weeks and different fractions of it were mixed with freshly prepared nylon-6 solution to get the electrospun mats. FE-SEM images of the mats indicated that the a large amount of sub-nanofibers (<50 nm in diameter) in the form of spider-net like structures were achieved by tailoring the amount of solvent degraded polymer solution in the freshly prepared nylon-6 solution. Large quantity of these ultrafine sub-nanofibers present in electrospun nylon-6 mats could increase its hydrophilicity and mechanical strength. The decreased average pore diameter and increased BET surface area of the mat, caused by spider-net like structure, can make it as a potential candidate for air/water filtration.

Fabrication of highly porous poly (ɛ-caprolactone) fibers for novel tissue scaffold via water-bath electrospinning.

Highly porous fibers were prepared by water-bath electrospinning from pure poly(ɛ-caprolactone) (PCL), and its blends with methoxy poly(ethylene glycol) (MPEG). These fibers were further analyzed by scanning electron microscopy (SEM), differential scanning calorimetry (DSC), X-ray diffraction (XRD), and gravimetric as well as contact angle measurement. SEM images showed that the fibers diameters as well as pores diameter on the fibers were affected by the weight ratio of MPEG/PCL. DSC and XRD not only revealed suppression of crystallinity of PCL but also indicated the presence of trace amount of MPEG in PCL water-bath collected fibers. The potential use of these hydrophilic porous electrospun fibrous mats as scaffolding materials was evaluated in vitro using mouse osteoblasts (MC3T3-E1) as reference cell lines. Cytotoxicity assessment of the fiber mats indicated that the porous electrospun mat containing trace amount of MPEG was nontoxic to the cell. Cell culture results showed that porous fibrous mats were good in promoting the cell attachment and proliferation. This novel electrospun matrix could be used as potential tissue scaffold material.

Effect of adhesive on the morphology and mechanical properties of electrospun fibrous mat of cellulose acetate.

Ultrafine fibers of cellulose acetate/poly(butyl acrylate) (CA/PBA) composite in which PBA acted as an adhesive and CA acted as a matrix, were successfully prepared as fibrous mat via electrospinning. The morphology observation from the electrospun CA/PBA composite fibers, after treatment with heat hardener, revealed that the fibers were cylindrical and had point-bonded structures. SEM, FT-IR spectra, Raman spectra, TGA analysis, and mechanical properties measurement were used to study the different properties of hybrid mats. The tensile strength of blend fibrous electrospun mats was found to be effectively increased. This resultant enhancement of the mechanical properties of polymer fibrous mats, caused by generating the point-bonded structures (due to adhesive), could increase the number of potential applications of mechanically weak electrospun CA fibers.

Photocatalytic and antibacterial properties of a TiO2/nylon-6 electrospun nanocomposite mat containing silver nanoparticles.

Silver-impregnated TiO(2)/nylon-6 nanocomposite mats exhibit excellent characteristics as a filter media with good photocatalytic and antibacterial properties and durability for repeated use. Silver nanoparticles (NPs) were successfully embedded in electrospun TiO(2)/nylon-6 composite nanofibers through the photocatalytic reduction of silver nitrate solution under UV-light irradiation. TiO(2) NPs present in nylon-6 solution were able to cause the formation of a high aspect ratio spider-wave-like structure during electrospinning and facilitated the UV photoreduction of AgNO(3) to Ag. TEM images, UV-visible and XRD spectra confirmed that monodisperse Ag NPs (approximately 4 nm in size) were deposited selectively upon the TiO(2) NPs of the prepared nanocomposite mat. The antibacterial property of a TiO(2)/nylon-6 composite mat loaded with Ag NPs was tested against Escherichia coli, and the photoactive property was tested against methylene blue. All of the results showed that TiO(2)/nylon-6 nanocomposite mats loaded with Ag NPs are more effective than composite mats without Ag NPs. The prepared material has potential as an economically friendly photocatalyst and water filter media because it allows the NPs to be reused.

Electrospun nylon-6 spider-net like nanofiber mat containing TiO(2) nanoparticles: a multifunctional nanocomposite textile material.

In this study, electrospun nylon-6 spider-net like nanofiber mats containing TiO(2) nanoparticles (TiO(2) NPs) were successfully prepared. The nanofiber mats containing TiO(2) NPs were characterized by SEM, FE-SEM, TEM, XRD, TGA and EDX analyses. The results revealed that fibers in two distinct sizes (nano and subnano scale) were obtained with the addition of a small amount of TiO(2) NPs. In low TiO(2) content nanocomposite mats, these nanofiber weaves were found uniformly loaded with TiO(2) NPs on their wall. The presence of a small amount of TiO(2) NPs in nylon-6 solution was found to improve the hydrophilicity (antifouling effect), mechanical strength, antimicrobial and UV protecting ability of electrospun mats. The resultant nylon-6/TiO(2) antimicrobial spider-net like composite mat with antifouling effect may be a potential candidate for future water filter applications, and its improved mechanical strength and UV blocking ability will also make it a potential candidate for protective clothing.