The aim of the present research work is to enhance the thermal and dynamic mechanical properties of Kevlar/Cocos nucifera sheath (CS)/epoxy composites with graphene nano platelets (GNP). Laminates were fabricated through the hand lay-up method followed by hot pressing. GNP at different wt.% (0.25, 0.5, and 0.75) were incorporated with epoxy resin through ultra-sonication. Kevlar/CS composites with different weight ratios (100/0, 75/25, 50/50, 25/75, 0/100) were fabricated while maintaining a fiber/matrix weight ratio at 45/55. Thermal degradation and viscoelastic properties were evaluated using thermogravimetric analysys (TGA), differential scanning calorimetric (DSC) analysis, and a dynamic mechanical analyser (DMA). The obtained results revealed that Kevlar/CS (25/75) hybrid composites at 0.75 wt.% of GNP exhibited similar thermal stability compared to Kevlar/epoxy (100/0) composites at 0 wt.% of GNP. It has been corroborated with DSC observation that GNP act as a thermal barrier. However, DMA results showed that the Kevlar/CS (50/50) hybrid composites at 0.75 wt.% of GNP exhibited almost equal viscoelastic properties compared to Kevlar/epoxy (100/0) composites at 0 wt.% GNP due to effective crosslinking, which improves the stress transfer rate. Hence, this research proved that Kevlar can be efficiently (50%) replaced with CS at an optimal GNP loading for structural applications.
The spread of graphene in low-density polyethylene (LDPE) improves LDPE/graphene nanocompounds' thermal/mechanical/electrical characteristics. The images of scanning electron microscopy (SEM) verify full graphene exfoliation at 1000 °C. Inclusion graphene develops crystallinity; increases the local order of lattice and thermal stability of LDPE/graphene nanocompounds. The consistent distributions and further inclusion of graphene caused the great heat breakdown strength, increasing heat breakdown activation energy and a superior melting point (Tm) for LDPE nanocompounds. Percolation occurs with the graphene incorporation of 0.5 wt%. The complex viscosity test showed Newtonian behavior for LDPE at a very low frequency. But, graphene inclusion to LDPE changed the viscosity performance from liquid-like to solid-like which caused a decrease in the melt flow rate (MFR) values for all LDPE/graphene nanocompounds.
Reduced graphene oxide nanosheet (RGO)/Pt nanocomposite have been successfully prepared through a facile chemical reduction method. The reduction of Pt precursor was carried out using sodium borohydride as the efficient chemical reductant. The morphology of RGO/Pt nanocomposite was investigated using high resolution transmission electron microscopy (HRTEM) and field emission scanning electron microscopy (FESEM). HRTEM analysis showed that platinum nanoparticles were homogenously distributed onto the surface of RGO. The electrochemical study proved that Pt nanoparticles were successfully incorporated onto RGO. Therefore, it can be concluded that the proposed method could provide well-dispersed of Pt nanoparticles onto RGO to form RGO/ Pt nanocomposite.
A one-pot green sonochemical process assisted by ascorbic acid as the reducing agent to produce highly reduced graphene oxide (rGO) decorated with silver nanoparticles (AgNPs) is demonstrated. A complete removal of oxygen-containing group in the GO sheets was confirmed by no observation of the peak corresponds to C-O, C=O and -OH bond. The unexpected decrease of peak intensity corresponds to sp2 hybridized C=C group is explained by a so-called bond polarity effect. The peak observed at ~400 nm seems to show the presence of AgNPs and the red shifting of C=C peak to ~270 nm after the introduction of ascorbic acid indicates the formation of highly reduced GO. The increase of AgNPs size and the crumpled silk-like morphology after the introduction of ascorbic acid also indicate the aggressive reduction of both AgNPs and GO. The increase of ID/IG ratio after the introduction of ascorbic acid seems to indicate the increase of the number of small sp2 domains, the presence of unrepaired defects and the restoration of the sp2 network. This work provides the promising green sonochemical approach by utilizing non-toxic and environmental-friendly reducing agent to produce highly reduced GO decorated with AgNPs for various applications.
We demonstrate the preparation of nanostructures cobalt oxide/reduced graphene oxide (Co3O4/rGO) nanocomposites by a simple one-step cost-effective hydrothermal technique for possible electrode materials in supercapacitor application. The X-ray diffraction patterns were employed to confirm the nanocomposite crystal system of Co3O4/rGO by demonstrating the existence of normal cubic spinel structure of Co3O4 in the matrix of Co3O4/rGO nanocomposite. FTIR and FT-Raman studies manifested the structural behaviour and quality of prepared Co3O4/rGO nanocomposite. The optical properties of the nanocomposite Co3O4/rGO have been investigated by UV absorption spectra. The SEM/TEM images showed that the Co3O4 nanoparticles in the Co3O4/rGO nanocomposites were covered over the surface of the rGO sheets. The electrical properties were analyzed in terms of real and imaginary permittivity, dielectric loss and AC conductivity. The electrocatalytic activities of synthesized Co3O4/rGO nanocomposites were determined by cyclic voltammetry and charge-discharge cycle to evaluate the supercapacitive performance. The specific capacitance of 754 Fg-1 was recorded for Co3O4/rGO nanocomposite based electrode in three electrode cell system. The electrode material exhibited an acceptable capability and excellent long-term cyclic stability by maintaining 96% after 1000 continuous cycles. These results showed that the prepared sample could be an ideal candidate for high-energy application as electrode materials. The synthesized Co3O4/rGO nanocomposite is a versatile material and can be used in various application such as fuel cells, electrochemical sensors, gas sensors, solar cells, and photocatalysis.
Cobalt incorporated sulfur-doped graphitic carbon nitride with bismuth oxychloride (Co/S-gC3N4/BiOCl) heterojunction is prepared by an ultrasonically assisted hydrothermal treatment. The heterojunction materials have employed in photoelectrochemical (PEC) water splitting. The PEC activity and stability of the materials are promoted by constructing an interface between the visible light active semiconductor photocatalyst and cocatalysts. The photocurrent density of Co-9% S-gC3N4/BiOCl has attained 393.0 μA cm-2 at 1.23 V vs. RHE, which is 7-fold larger than BiOCl and ~3-fold higher than 9% S-gC3N4/BiOCl. The enhanced PEC activity can be attributed to the improved electron-hole charge separation and the boosted charge transfer is confirmed by photoluminescence (PL) and electrochemical impedance spectroscopy (EIS) analysis. The fabricated Co/S-gC3N4/BiOCl nanohybrid material has exhibited high stability of up to 10,800 s (3 h) at 1.23 V vs. RHE during PEC water splitting reaction and the obtained photo-conversion efficiency is 3.7-fold greater than S-gC3N4/BiOCl and 17-fold higher than BiOCl. The FESEM and HRTEM images have revealed the formation of heterojunction interface between S-gC3N4 and BiOCl and the elemental mapping has confirmed the presence of cobalt over S-gC3N4/BiOCl. The heterojunction interface has facilitated the photo-excited charge separation and transport across the electrode/electrolyte interface and also the flat-band potential, which is confirmed by Mott-Schottky analysis.
One of the most crucial attributes of synthetic organic chemistry is to design organic reactions under the facets of green chemistry for the sustainable production of chemicals. Thus, due to the intensified environmental and safety concern, the need for new technologies for conducting chemical transformation has grown. In this regard, there is enormous interest in the use of heterogeneous catalysts as they generally avoid the generation of waste, require fewer toxic reagents, as well as entail easier separation and recycling of the catalyst. α,β-Unsaturated acids have been widely used in various industrial applications and have been identified as one of the most promising chemicals obtained via the Knoevenagel condensation reaction. This review aims to discuss the most pertinent heterogeneous catalytic systems such as zeolites, mesoporous silica, ionic liquids, metal oxides, and graphitic carbon nitride-based catalysts in the Knoevenagel reaction. Ultimately, this review focuses not only on the catalyst but also provides an overall idea and guide for the preparation of new catalysts with outstanding properties by looking at the chemical and engineering aspects such as the reaction conditions and the mechanisms.
The development of semiconductor heterojunctions is a promising and yet challenging strategy to boost the performance in photoelectrochemical (PEC) water splitting. This paper describes the fabrication of a heterojunction photoanode by coupling α-Fe2O3 and g-C3N4via aerosol-assisted chemical vapour deposition (AACVD) followed by spin coating and air annealing. Enhanced PEC performance and stability are observed for the α-Fe2O3/g-C3N4 heterojunction photoanode in comparison to pristine α-Fe2O3 and the reason is systematically discussed in this paper. Most importantly, the fabricated α-Fe2O3/g-C3N4 film shows impressive stability, retaining more than 90% of the initial current over 12 h operating time. The excellent stability of the heterojunction photoanode is achieved due to the unique nanoflake structure of α-Fe2O3 induced by AACVD. This nanostructure promotes good adhesion with the g-C3N4 particles, as the particles tend to be trapped within the α-Fe2O3 valleys and eventually create strong and large interfacial contacts. This leads to improved separation of charge carriers at the α-Fe2O3/g-C3N4 interface and suppression of charge recombination in the photoanode, which are confirmed by the transient decay time, charge transfer efficiency and electrochemical impedance analysis. Our findings demonstrate the importance of nanostructure engineering for developing heterojunction structures with efficient charge transfer dynamics.
This work aims to give insight on the effect of accelerated weathering, i.e., the combination of ultraviolet (UV) exposure and water spraying, on the visual and mechanical properties of basalt fiber reinforced polymer (BFRP) composites. The solvent exchange method, sonication and high shear milling technique were used to prepare the nanocomposite laminates. Three types of laminates were fabricated, i.e., unmodified BFRP, nanosilica modified BFRP and graphene nanoplatelet (GNP) modified BFRP composites with the total fiber loading of 45 wt.%. Glass fiber reinforced polymer (GFRP) laminate was also prepared for performance comparison purposes between the natural and synthetic fibers. The laminates were exposed to UV with a total weathering condition of 504 h using a Quantum-UV accelerated weathering tester. The weathering condition cycle was set at 8 h 60 °C UV exposure and 4 h 50 °C condensation. The discoloration visual inspection on the tested specimen was observed under the optical microscope. The obtained results showed that the UV exposure and water absorption caused severe discoloration of the laminates due to photo-oxidation reaction. The effect of weathering conditions on tensile and flexural properties of unmodified BFRP composites indicated that the UV exposure and water absorption caused reduction by 12% in tensile strength and by 7% in flexural strength. It is also found that the reduction in tensile and flexural properties of nanomodified BFRP composites was smaller than the unmodified system. It concluded from this work, that the mineral based composites (i.e., BFRP) has high potential for structural applications owing to its better properties than synthetic based composites (i.e., GFRP).
A novel nanocomposite of MGO-NGC, composed of magnetic Fe3O4 nanoparticles (M), graphene oxide (GO), and N-methyl-d-glucamine functionalized calix[4]arene (NGC), was synthesized and applied as an effective adsorbent for the removal of two selected pesticides, namely hexaconazole and chlorpyrifos from water samples. The adsorbent was characterized by FTIR, SEM, EDX, TEM, and XRD. The main parameters affecting the adsorption process such as adsorbent dosage, pH of sample solution, salt effect, pesticide concentration, and adsorption time were investigated. The data from kinetic studies fitted well to the pseudo-second order kinetic model with R2 > 0.99. Among the isotherm models of Langmuir, Freundlich, Temkin, and Dubinin-Radushkevich, the Langmuir isotherm fitted well to the adsorption process and demonstrated the monolayer adsorption pattern of the pesticides. Moreover, high adsorption capacities of 78.74 and 93.46 mg g-1 were obtained for chlorpyrifos and hexaconazole, respectively. Thermodynamic and free energy data indicated the physisorption mechanism for the adsorption process. The new adsorbent can be employed as an efficient, environment friendly, and highly reusable alternative for the removal of chlorinated pesticides from aqueous media.
In this study, reduced graphene oxide (RGO)/polymethyl methacrylate (PMMA) nanocomposites were prepared by employing in situ polymerization and solution blending methods. In terms of mechanical properties, RGO loading increased the Young's modulus but decreased the elongation at break for RGO/PMMA nanocomposites. Tensile strength for solution blended RGO/PMMA nanocomposites increased after adding 0.5 wt % RGO, which was attributed to the good dispersion of RGO in the nanocomposites as evidenced from SEM and TEM. Solar energy conversion efficiency measurement results showed that the optimum concentration of RGO in the RGO/PMMA nanocomposites was found to be 1.0 wt % in order to achieve the maximum solar energy conversion efficiency of 25%. In the present study, the solution blended nanocomposites exhibited better overall properties than in situ polymerized nanocomposites owing to the better dispersion of RGO in solution blending. These findings would contribute to future work in search of higher conversion efficiency using nanocomposites.
In the interest of the trend towards miniaturization of electronic gadgets, this study demonstrates a high-density data storage device with a very simple three-stacking layer consisting of only one charge trapping layer. A simple solution-processed technique has been used to fabricate the tristable non-volatile memory. The three-stacking layer was constructed in between two metals to form a two-terminal metal-insulator-metal structure. The fabricated device showed a large multilevel memory hysteresis window with a measured ON/OFF current ratio of 107 that might be attributed to the high charge trapped in molybdenum disulphide (MoS2) flakes-graphene quantum dots (GQDs) heterostructure. Transmission electron microscopy was performed to examine the orientation of MoS2-GQD and mixture dispersion preparation method. The obtained electrical data was used further to speculate the possible transport mechanisms through the fabricated device by a curve fitting technique. Also, endurance cycle and retention tests were performed at room temperature to investigate the stability of the device.
Agglomeration and restacking can reduce graphene oxide (GO) activity in a wide range of applications. Herein, GO was synthesized by a modified Hummer's method. To minimize restacking and agglomeration, in situ chemical oxidation polymerization was carried out to embed polyaniline (PANI) chains at the edges of GO sheets, to obtain GO-PANI nanocomposite. The GO-PANI was tested for the adsorptive removal of brilliant green (BG) from an aqueous solution through batch mode studies. Infrared (FT-IR) analysis revealed the dominance of hydroxyl and carboxylic functionalities over the GO-PANI surface. Solution pH-dependent BG uptake was observed, with maximum adsorption at pH 7, and attaining equilibrium in 30 min. The adsorption of BG onto GO-PANI was fit to the Langmuir isotherm, and pseudo-second-order kinetic models, with a maximum monolayer adsorption capacity (qm) of 142.8 mg/g. An endothermic adsorption process was observed. Mechanistically, π-π stacking interaction and electrostatic interaction played a critical role during BG adsorption on GO-PANI.
This paper describes the synthesis of graphene-based activated carbon from carbonaceous rice straw fly ash in an electrical furnace and the subsequent potassium hydroxide extraction. The produced graphene has a proper morphological structure; flakes and a rough surface can be observed. The average size of the graphene was defined as up to 2000 nm and clarification was provided by high-resolution microscopes (FESEM and FETEM). Crystallinity was confirmed by surface area electron diffraction. The chemical bonding from the graphene was clearly observed, with -C=C- and O-H stretching at peaks of 1644 cm-1 and 3435 cm-1, respectively. Impurities in the graphene were found using X-ray photoelectron spectroscopy and energy dispersive X-ray spectroscopy. The measured size, according to zeta-potential analysis, was 8722.2 ± 25 nm, and the average polydispersity index was 0.576. The stability of the mass reduction was analyzed by a thermogravimetric at 100 °C, with a final reduction of ~ 11%.
In this work, fibrous silica-titania (FST) was successfully prepared by the microemulsion method prior to the addition of three types of carbonaceous materials: graphitic-carbon nitride, g-C3N4 (CN), graphene nanoplatelets (GN), and multi-wall carbon nanotubes, MWCNT (CNT), via a solid-state microwave irradiation technique. The catalysts were characterized using XRD, FESEM, TEM, FTIR, UV-Vis DRS, N2 adsorption-desorption, XPS and ESR, while their photoactivity was examined on the degradation of toxic 2-chlorophenol (2-CP). The result demonstrated that the initial reaction rate was in the following order: CNFST (5.1 × 10-3 mM min-1) > GNFST (2.5 × 10-3 mM min-1) > CNTFST (2.3 × 10-3 mM min-1). The best performance was due to the polymeric structure of g-C3N4 with a good dispersion of C and N on the surface FST. This dispersion contributed towards an appropriate quantity of defect sites, as a consequence of the greater interaction between g-C3N4 and the FST support, that led to narrowed of band gap energy (2.98 eV to 2.10 eV). The effect of scavenger and ESR studies confirmed that the photodegradation over CNFST occurred via a Z-scheme mechanism. It is noteworthy that the addition of green carbonaceous materials on the FST markedly enhanced the photodegradation of toxic 2-CP.
Herein, we performed an encyclopedic analysis on the photoelectrocatalytic hydrogen production of BiVO4/g-C3N4 decorated with reduced graphene oxide (RGO) or graphene quantum dots (GQDs). The differences between RGO and GQDs as an electron mediator was revealed for the first time in the perspective of theoretical DFT analysis and experimental validation. It was found that the incorporation of GQDs as an electron mediator promotes better photoelectrocatalytic hydrogen performance in comparison to the RGO. The addition of GQD can significantly improve the activity by 25.2 and 75.7% in comparison to the BiVO4/RGO/g-C3N4 and binary composite samples, respectively. Correspondingly, the BiVO4/GQD/g-C3N4 attained the highest photocurrent density of 19.2 mA/cm2 with an ABPE of 0.57% without the presence of any sacrificial reagents. This enhancement is stemming from the low photocharge carrier transfer resistance which was further verified via DFT study. The DFT analysis revealed that the BiVO4/GQD/g-C3N4 sample shared their electronic cloud density through orbital hybridization while the BiVO4/RGO/g-C3N4 sample show less mutual sharing. Additionally, the charge redistribution of the GQDs-composite at the heterostructure interface articulates a more stable and stronger heterojunction than the RGO-composite. Notably, this study provides new insights on the effect of different carbonaceous materials (RGO and GQDs) which are often used as an electron mediator to enhance photocatalytic activity.
Photocatalysts provide excellent potential for the full removal of organic chemical pollutants as an environmentally friendly technology. It has been noted that under UV-visible light irradiation, nanostructured semiconductor metal oxides photocatalysts can degrade different organic pollutants. The Sn6SiO8/rGO nanocomposite was synthesized by a hydrothermal method. The Sn6SiO8 nanoparticles hexagonal phase was confirmed by XRD and functional groups were analyzed by FT-IR spectroscopy. The bandgap of Sn6SiO8 nanoparticles (NPs) and Sn6SiO8/GO composites were found to be 2.7 eV and 2.5 eV, respectively. SEM images of samples showed that the flakes like morphology. This Sn6SiO8/rGO nanocomposite was testing for photocatalytic dye degradation of MG under visible light illumination and excellent response for the catalysts. The enhancement of photocatalytic performance was mainly attributed to the increased light absorption, charge separation efficiency and specific surface area, proved by UV-vis DRS. Further, the radical trapping experiments revealed that holes (h+) and superoxide radicals (·O-₂) were the main active species for the degradation of MG, and a possible photocatalytic mechanism was discussed.
Polymethyl methacrylate (PMMA) bone cements (BCs) have some drawbacks, including limited bioactivity and bone formation, as well as inferior mechanical properties, which may result in failure of the BC. To deal with the mentioned issues, novel bioactive polymethyl methacrylate-hardystonite (PMMA-HT) bone cement (BC) reinforced with 0.25 and 0.5 wt% of carbon nanotube (CNT) and reduced graphene oxide (rGO) was synthesized. In this context, the obtained bone cements were evaluated in terms of their mechanical and biological characteristics. The rGO reinforced bone cement exhibited better mechanical properties to the extent that the addition of 0.5 wt% of rGO where its compressive and tensile strength of bioactive PMMA-HT/rGO cement escalated from 92.07 ± 0.72 MPa, and 40.02 ± 0.71 MPa to 187.48 ± 5.79 MPa and 64.92 ± 0.75 MPa, respectively. Besides, the mechanisms of toughening, apatite formation, and cell interaction in CNT and rGO encapsulated PMMA have been studied. Results showed that the existence of CNT and rGO in BCs led to increase of MG63 osteoblast viability, and proliferation. However, rGO reinforced bone cement was more successful in supporting MG63 cell attachment compared to the CNT counterpart due to its wrinkled surface, which made a suitable substrate for cell adhesion. Based on the results, PMMA-HT/rGO can be a proper bone cement for the fixation of load-bearing implants.
Metal ions homeostasis plays an important role in biological processes. The ability to detect the concentration of metal ions in biological fluids is often challenged by the obvious interference or competitive binding nature of other alkaline metals ions. Common analytical techniques employed for metal ions detection are electrochemical, fluorescence and colorimetric methods. However, most reported metal ions sensors are complicated, time-consuming and involve costly procedures with limited effectiveness. Herein, a nanobiosensor for detecting sodium and potassium ions using folic acid-functionalised reduced graphene oxide-modified RNase A gold nanoclusters (FA-rGO-RNase A/AuNCs) based on fluorescence "turn-off/turn-on" is presented. Firstly, a facile and optimised protocol for the fabrication of RNase A/AuNCs is developed. The activity of RNase A protein after the formation of RNase A/AuNCs is studied. RNase A/AuNCs is then loaded onto FA-rGO, in which FA-rGO is used as a potential carrier and fluorescence quencher for RNase A/AuNCs. Finally, a fluorescence "turn-on" sensing strategy is developed using the as-synthesised FA-rGO-RNase A/AuNCs to detect sodium and potassium ions. The developed nanobiosensor revealed an excellent sensing performance and meets the sensitivity required to detect both sodium and potassium ions. To the best of our knowledge, this is the first work done on determining the RNase A protein activity in RNase A/AuNCs and exploring the potential application of RNase A/AuNCs as a metal ion sensor. This work serves as a proof-of-concept for combining the potential of drug delivery, active targeting and therapy on cancer cells, as well as biosensing of metal ions into a single platform.
This study aimed to analyze the environmental impacts of the oxidative desulfurization (ODS) process catalyzed by metal-free reduced graphene oxide (rGO) through life cycle assessment (LCA). The environmental impacts study containing the rGO production process, the ODS process, the comparison of different oxidants and solvents was developed. This study was performed by using ReCiPe 2016 V1.03 Hierarchist midpoint as well as endpoint approach and SimaPro software. For the production of 1 kg rGO, the results showed that hydrochloric acid (washing), sulfuric acid (mixing), hydrazine (reduction) and electricity were four main contributors in this process, and this process showed a significant impact on human health 14.21 Pt followed by ecosystem 0.845 Pt and resources 0.164 Pt. For the production of 1 kg desulfurized oil (400 ppm), main environmental impacts were terrestrial ecotoxicity (43.256 kg 1,4-DCB), global warming (41.058 kg CO2), human non-carcinogenic toxicity (19.570 kg 1,4-DCB) and fossil resource scarcity (13.178 kg oil), and the main contributors were electricity, diesel oil and acetonitrile. The whole ODS process also showed a greatest effect on human health. For two common oxidants hydrogen peroxide and oxygen used in ODS, hydrogen peroxide showed a greater impact than oxygen. On the other hand, for three common solvents employed in ODS, N-methyl-2-pyrrolidone had a more serious impact on human health followed by acetonitrile and N,N-dimethylformamide. As such, LCA results demonstrated the detailed environmental impacts originated from the catalytic ODS, hence elucidating systematic guidance for its future development toward practicality.